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2021 135 Anna V áblo a 3d, 4 and 3d-4 complexes based on selec ed N,O- and O- dono ligands Di ec o /es Fal ello, La y Ce nak, Ju aj © Uni e sidad de Za agoza Se icio de Publicaciones ISSN 2254-7606 Anna V áblo a 3D, 4F AND 3D-4F COMPLEXES BASED ON SELECTED N,O- AND O-DONOR LIGANDS Di ec o /es Fal ello, La y Ce nak, Ju aj Tesis Doc o al Au o 2021 UNIVERSIDAD DE ZARAGOZA Escuela de Doc o ado P og ama de Doc o ado en Química Ino gánica Reposi o io de la Uni e sidad de Za agoza – Zaguan h p://zaguan.uniza .es PAVOL JOZEF ŠAFÁRIK UNIVERSITY IN KOŠICE FACULTY OF SCIENCE & UNIVERSITY OF ZARAGOZA FACULTY OF SCIENCE 3d, 4 AND 3d-4 COMPLEXES BASED ON SELECTED N,O- AND O-DONOR LIGANDS 2020 Mg . Anna VRÁBLOVÁ PAVOL JOZEF ŠAFÁRIK UNIVERSITY IN KOŠICE FACULTY OF SCIENCE & UNIVERSITY OF ZARAGOZA FACULTY OF SCIENCE 3d, 4 AND 3d-4 COMPLEXES BASED ON SELECTED N,O- AND O-DONOR LIGANDS DISSERTATION THESIS S udy p og am: Ino ganic Chemis y Ins i u e: Ins i u e o Chemis y / Depa men o Ino ganic Chemis y Supe iso s: p o . Ju aj Če nák, D Sc. p o . Law ence R. Fal ello Košice 2020 Mg . Anna VRÁBLOVÁ Acknowledgemen s A his poin , I would like o hank my supe iso s Ju aj Če nák and Law ence R. Fal ello o hei p o essional leade ship and scien i ic suppo . I am much obliga ed also o Milag os Tomás o he sugges i e ideas and expe imen al ad ice. Special hanks belong o Isabel Mayo al who has ne e e used o help in he labo a o y o whe e e he help was needed. I would like o acknowledge Roman Boča and his eam o he magne ic measu emen s and in e p e a ions o hei esul s. I hank bo h uni e si ies, P. J. Ša á ik Uni e si y in Košice (Slo akia) and Uni e si y o Za agoza (Spain) o he unpa alleled oppo uni y o unde go he double deg ee doc o a e p og amme. Join doc o a e opens no only bo de s bu also ou minds. My esea ch and a elling was inancialy suppo ed by Na ional Schola ship P og amme (Slo akia), E asmus p og amme (P. J. Ša á ik Uni e si y in Košice, Slo akia), Slo ak g an agencies (APVV-14-0078, APVV-14-0073, APVV-18-0016, VEGA 1/0534/16, VEGA 1/0063/17 and VEGA 1/0075/13), P. J. Ša á ik Uni e si y (VVGS-PF-2016-72623 and VVGS-PF-2018-777), Minis e io de Ciencia, Inno ación y Uni e sidades (Spain, G an s MAT2011-27233-C02-01, MAT2011-27233-C02-02, MAT2015-68200-C2-1-P, PGC2018-093451-B-I00), Eu opean FEDER unds (Spain), he Dipu ación Gene al de A agón (Spain, P ojec M4, E11_17R) and he p ojec NFP313010V954 o call OPVaI-VA/DP/2018/1.1.3-07 (Spain). Abs ac The p esen wo k is ocused on he s udy o single-molecule magne s based on selec ed ansi ion me als and lan hanides using a selec ed Schi base ligand. The i s pa deals wi h he heo e ical in e p e a ion o he magne ic phenomenon o SMM as well as he coo dina ion and magne ic p ope ies o complexes con aining cen al a oms Ni(II), Co(II)/(III), Ce(III), Gd(III) and Dy(III). In he expe imen al pa , he me hod o p epa a ion o he equi ed complexes was de e mined in he i s place - he so-called "sel -assembly" me hod. Acco ding o he syn he ic p ocedu es hus de e mined, 21 compounds we e p epa ed, which we e physically and chemically cha ac e ized and hei c ys al s uc u e was de e mined by X- ay s uc u e analysis. One chap e is ocused on he c ys allog aphic s udy o polymo phism, whe e FIM me hods and analysis o Hi sh eld su aces we e used o a mo e de ailed examina ion o wo polymo phs [CoIII2(o- an-en)3]·4CH3CN. The wo k also includes a c ys allog aphic s udy o a opo ac ic eac ion o he SC-SC (Single C ys al- o-Single C ys al) ype in which he complex [Ni(o- an-en)DyCl3(H2O)] dehyd a es a a highe empe a u e and subsequen ly dime izes o o m a new complex [Ni2(o- an-en)2Dy2Cl6]. F om he p epa ed subs ances, 4 complexes we e selec ed and subjec ed o magne ic examina ion wi h espec o SMM p ope ies. Fo all ou subs ances, he slow elaxa ion o magne iza ion, ypical o single-molecule magne s, was con i med. The mos signi ican esul was he obse a ion o slow magne ic elaxa ion in a Ni-Gd sample, whe e he Ni(II) cen al a om is diamagne ic and Gd(III) is gene ally magne ically iso opic. The geome y and he elec on densi y o he coo dina ion si es has been p o ed o exe a e y impo an in luence on he SMM beha iou o lan hanide ions which has con ibu ed o he heo e ical knowledge o SMMs. Abs ak P edkladaná p áca je zame aná na š údium jednomolekulo ých magne o na báze yb aných p echodných ko o a lan anoido s použi ím yb aného ligandu Schi o ej zásady. P á časť p áce sa enuje eo e ickému opisu jednomolekulo ého magne izmu ako aj koo dinačnej chémii a magne ickým las nos iam komplexo obsahujúcich cen álne a ómy Ni(II), Co(II)/(III), Ce(III), Gd(III) a Dy(III). V ámci expe imen álnej čas i bola najp yp aco aná me óda p íp a y požado aných komplexo – z . „sel -assembly“ me óda. Podľa ak o u čených syn e ických pos upo bolo p ip a ených 21 lá ok, k o é boli yzikálne a chemicky cha ak e izo ané a pomocou g. š uk ú nej analýzy bola s ano ená ich k yš álo á š uk ú a. Jedna kapi ola p áce je zame aná na k yš alog a ickú š údiu polymo ie, kde sa použili me ódy FIM a analýza Hi sh eldo ých po cho na de ailnejšie p eskúmanie d och polymo o [CoIII2(o- an-en)3]·4CH3CN. P áca zahŕňa aj k yš alog a ické š údium opo ak ickej eakcie ypu SC-SC (Single C ys al- o-Single C ys al), p i k o ej sa komplex [Ni(o- an- en)DyCl3(H2O)] p i yššej eplo e dehyd a uje a jej dôsledku dime izuje za zniku no ého komplexu [Ni2(o- an-en)2Dy2Cl6]. Spomedzi p ip a ených lá ok boli yb ané 4 komplexy, u k o ých sa š udo ali ich magne ické las nos i s ohľadom na ich SMM cha ak e . U še kých š y och lá kach bola po dená pomalá elaxácia magne izácie, k o á je ypická p e jednomolekulo é magne y. Naj ýznamnejším ýsledkom bolo pozo o anie pomalej magne ickej elaxácie Ni-Gd zo ke, kde cen álny a óm Ni(II) je diamagne ický a Gd(III) je o šeobecnos i magne icky izo opný. Ukázalo sa, že geome ia a elek óno á hus o a koo dinačných mies majú eľmi dôleži ý ply na SMM sp á anie lan anoido ých ióno , čo po ispelo k doplneniu eo e ických pozna ko o SMMs. Resumen El p esen e abajo se cen a en el es udio de imanes monomolecula es (SMM) basados en me ales de ansición y lan ánidos seleccionados u ilizando un ligando base de Schi seleccionado. La p ime a pa e abo da la in e p e ación eó ica del enómeno magné ico de SMMs, así como las p opiedades de coo dinación y magne ismo de los complejos que ienen como á omos cen ales Ni(II), Co(II)/(III), Ce(III), Gd(III) y Dy(III). En la pa e expe imen al, el mé odo de p epa ación de los complejos se es ableció en p ime luga , el llamado mé odo de "au oensamblaje". De acue do con los p ocedimien os sin é icos así de e minados, se p epa a on 21 compues os, que ue on ca ac e izados ísicamen e y químicamen e median e las écnicas habi uales, mien as se analiza on sus es uc u as c is alinas median e la di acción de ayos X en monoc is al. Un capí ulo se cen a en el es udio c is alog á ico del polimo ismo, donde se u iliza on los mé odos FIM ( ull in e ac ion mapping) y el análisis de las supe icies de Hi sh eld pa a una explo ación de allada de dos polimo os de [CoIII2(o- an-en)3]·4CH3CN. El abajo ambién incluye el es udio c is alog á ico de una eacción opo ác ica del ipo SC-SC (Single C ys al- o-Single C ys al) en el que el complejo [Ni(o- an- 11 2 Theo e ical Backg ound 2.1 Molecula Magne ism In he las h ee decades, i s - ow ansi ion me als such as Mn(III), Fe(III), Fe(II), Co(II) and Ni(II) we e s udied om he poin o iew o molecula magne ism. Undoub edly, he mos in ensi e a en ion is paid o so-called single-molecule magne s (SMMs) which a e molecula species ha display se e al cha ac e is ic magne ic p ope ies such as unnelling o he magne iza ion and slow magne iza ion elaxa ion. The undamen al aspec o SMMs is ha hey can be magne ized by an ex e nal magne ic ield and a e he ield is emo ed hey a e able o p ese e his magne iza ion o a ce ain ime (a a ce ain empe a u e). This magne ic hys e esis is called slow elaxa ion o magne iza ion (Fig. 2.1.1. igh ). As his elaxa ion has a pu ely molecula o igin, he ma e ial is a so-called single-molecule magne . When a complex exhibi s such beha iou , bu he e is a me al ion, hey a e o en e e ed o as single-ion magne s (SIMs) and al e na i ely o chain-like s uc u es – single-chain magne s (SCMs). These ma e ials can be used in spin-based elec onic de ices o in o ma ion s o age o high densi y. Figu e 2.1.1 Le : The c ys al s uc u e o [Mn12(CH3COO)16(H2O)4O12]·2CH3COOH·4H2O: p ojec ion on he (001) plane [Lis, 1980]. Righ : Hys e esis loops o [Mn12(CH3COO)16(H2O)4O12]·2CH3COOH·4H2O eco ded pa allel o he c axis wi h a SQUID magne ome e a 2.2 K ( ull ci cles) and 2.8 K (emp y ci cles). The do ed lines a e only a guide o he eye [Sessoli e al., 1993]. 12 Slow elaxa ion o magne iza ion can be desc ibed by he simple ‘double-well’ diag am (Scheme 2.1.2.). All he ene gy le els MS a e localised in wo equal wells, –MS in he le , +MS in he igh one. When no ex e nal ield is applied all he ene gy le els o ±MS a e degene a e pai s (excep MS = 0) and he wells a e equally popula ed. In an ex e nal magne ic ield pa allel o he magne iza ion axis he –MS le els a e s abilised o he p ejudice o hose o +MS (no e: applied ield is pa allel o he z axis, +MS le els co espond o a p ojec ion o he magne iza ion an ipa allel o he ield and –MS le els co espond o magne iza ion pa allel o he applied ex e nal ield). When he ex e nal ield is emo ed he sys em e u ns o he mal equilib ium. Scheme 2.1.2 ‘Double well’ diag am showing magne iza ion and elaxa ion p ocess in SMM. Scheme 2.1.3 Schema ic mechanisms o elaxa ion p ocesses: QTM, TA-QTM, O bach and Raman p ocess. 13 The elaxa ion pa hway can di e om one sys em o ano he . The e a e se e al p ocesses known – di ec , O bach, Raman, quan um unnelling and he mally assis ed quan um unnelling o magne iza ion (Scheme 2.1.3). The magne iza ion can unnel h ough he aniso opy ba ie be ween g ound s a es o be ween exci ed s a es ia he mally assis ed mechanisms. An O bach p ocess in ol es abso p ion o a la ice phonon ollowed by phonon emission and elaxa ion om an exci ed s a e, while in a Raman p ocess he elaxa ion occu s om a i ual s a e. The size o he e ec i e ene gy ba ie (Ue ) is a ec ed by wo pa ame e s, namely he g ound spin s a e (S) and he magne ic aniso opy pa ame e (D): 𝑈𝑒𝑓𝑓 = |𝐷|𝑆2 (in ege spins) 𝑈𝑒𝑓𝑓 = |𝐷|(𝑆2−1 4) (non-in ege spins) By he simple app oach, he la ge he ene gy ba ie Ue be ween e e sal spin le els he longe will be he obse ed elaxa ion ime. In gene al, a high spin g ound s a e combined wi h a s ong magne ic aniso opy is he equi ed ea u e o SMMs [Neese & Pan azis, 2011]. Magne ic aniso opy is go e ned by he axial D and hombic E ze o- ield spli ing pa ame e s acco ding o he Hamil onian 𝐻 =𝐷𝑆𝑧2+𝐸(𝑆𝑥 2− 𝑆𝑦 2) whe e S is he o al spin quan um numbe . These wo pa ame e s e lec he dis o ion o symme y a ound he magne ic cen e and co ela e wi h analogous s uc u al pa ame e s Ds and Es desc ibing he s uc u al dis o ion o he cen al ion [I aníko á e al., 2006]. 2.2 In oduc ion o Lan hanides o Molecula Magne ism In con as o ansi ion me als, elemen s play an impo an ole in single- molecule magne ism due o hei highly aniso opic magne ic momen s. A iew o he asphe ici y o he 4 elec on densi y acili a es unde s anding o he magne ic aniso opy o lan hanide ions [Jiang & Qin, 2015] (Fig. 2.2.1). 14 Fig. 2.2.1 The 4 -shell elec on cloud shapes o Ln(III) ions in hei Ising limi s a e. Ce(III), P (III), Nd(III), Tb(III), Dy(III) and Ho(III) a e so-called obla e ions (axially comp essed), Pm(III), Sm(III), E (III), Tm(III) and Yb(III) a e p ola e ions (axially elonga ed) and Eu(III), Gd(III) and Lu(III) a e iso opic ions (sphe ical) [Jiang & Qin, 2015]. Figu e 2.2.2 Uppe : Scheme o he molecula s uc u e o [Pc2Ln]- (Ln = Tb o Dy). Lowe : Plo s o ( op) χM´T and (bo om) χM´´/ χM agains empe a u e T, whe e χM´, χM´´, and χM a e in-phase-AC, ou -o -phase-AC, and DC mola magne ic suscep ibili ies, espec i ely, o a powde sample o [Pc2Ln]-·TBA+ (le : Ln = Tb; igh : Ln = Dy; open ma ks) and co esponding complex dilu ed in [Pc2Y]-·TBA+ ( illed ma ks) measu ed in a 3.5 G AC magne ic ield oscilla ing a indica ed equencies [Ishikawa e al., 2003]. 15 Conce ning he igh choice o lan hanides, 4 ions wi h he highes magne ic aniso opy and highes spin alue a e he mos app op ia e o enhancing he elaxa ion ime in SMM. The i s lan hanide single-molecule magne was desc ibed in 2003 by Ishikawa e al.; ph halocyanine double-decke complexes o Tb(III) and Dy(III) showed slow magne iza ion elaxa ion in he empe a u e anges signi ican ly highe han hose o he ansi ion me al clus e SMMs and hus a new class o magne s a he molecula le el was es ablished [Ishikawa e al., 2003] (Fig. 2.2.2). F om hen on, he numbe o s udies o lan hanide based SMMs inc eased apidly; he e a e mo e han 1 500 published a icles up- o-now and hey a e s ill a cu en opic among ma e ials scien is s. Mo eo e , he magne ic p ope ies o lan hanide ions a e di e en om hose o ansi ion me al ions, whose magne ism mainly comes om spin magne ic momen , he o bi al con ibu ion being in luenced by he ligand ield. In con as o ha beha iou , he magne ic momen o he Ln(III) ions is essen ially independen o en i onmen , he e o e one canno dis inguish be ween coo dina ion geome ies as is common o ansi ion me als, o example, in he case o oc ahed al, e ahed al and squa e plana NiII complexes. Two pa ame e s ha a ec he size o he e ec i e ene gy (aniso opic) ba ie (Ue ) o SMMs based on ansi ion me als, namely he g ound spin s a e (S) and he magne ic aniso opy pa ame e (D), a e in e sely p opo ional o each o he which p e en s a signi ican imp o emen in SMM p ope ies [Ahmed e al., 2014]. Wi h ega d o ha a combina ion o lan hanides and ansi ion me al ions has been used in an e o o inc ease maximal magne ic aniso opy. The o he bene i o such s uc u es is he al eady obse ed e omagne ic coupling be ween Cu(II)–Ln(III) and Ni(II)–Ln(III) ions o e ing g ea po en ial o SMM s udy [Ahmed e al., 2014]. The fi s in es iga ion o he magne ic p ope ies o a 3d–4 he e ome allic complex is due o Bencini e al., who obse ed and cha ac e ized he e omagne ic in e ac ion be ween Cu(II) and Gd(III) [Bencini e al., 1985]. Resea che s began o see he 3d-4 complexes om he molecula magne ism poin o iew only in he las decade o wo. Osa e al. es ablished a new class o SMMs by publishing wo cyclic 3d-4 e anuclea compounds, namely [CuLTb(h ac)2]2 and [CuLDy(h ac)2]2 (H2L = 1-(2- hyd oxybenzamido)-2-(2-hyd oxy-3-me hoxy-benzylideneamino)e hane [Osa e al., 2004]. 16 Howe e , esea ch in ecen yea s has e ealed a ew examples o a signi ican educ ion in quan um unnelling magne iza ion (QTM) due o non-negligible magne ic exchange in e ac ion be ween lan hanide and ansi ion me al ions [Langley e al., 2013]. On he o he hand, ecen s udy on he 3d-4 complexes wi h diamagne ic 3d me al ions such as zinc(II) o cobal (III) showed he enhancemen o he Ue ba ie compa ed o hei mononuclea lan hanide analogues [Fondo e al., 2017]; i was sugges ed ha he p esence o a diamagne ic 3d ca ion nea he lan hanide cen al a om, bo h sha ing oxygen b idging a oms, induces a la ge cha ge pola iza ion on he b idging oxygen a om ha a ou s an inc ease in he Ue ba ie . This obse a ion in okes a new s a egy in designing he 3d-4 complexes wi h diamagne ic 3d ions [Langley e al., 2012; Langley e al., 2013; Upadhyay e al., 2014; Sun e al., 2016; Upadhyay e al., 2017]. Fu he possibili ies o c ys allog aphic and magne ic s udies eme ge wi h he syn hesis o complexes wi h non-equimola a ios o 3d and 4 ions. In 1985, Bencini e al. i s epo ed he c ys al s uc u es along wi h hei magne ic p ope ies o wo he e o inuclea 3d-4 -3d complexes, obse ing e omagne ic in e ac ion be ween adjacen Cu(II) and Gd(III) ions [Bencini e al., 1985]. Fu he esea ch o such inuclea complexes wi h diamagne ic Ln(III) ions demons a ed also he p esence o he in e ac ion be ween wo e minal ansi ion me als [Shiga e al., 2007]. In he pas wo decades o so, he e obinuclea complexes we e used as building blocks in designing ex ended s uc u es ia addi ional anionic ligands b idging monome ic uni s. This e m also encompasses oligonuclea complexes, mul ime allic complexes, coo dina ion polyme s, mul idimensional a ays and ela ed s uc u es [Gheo ghe e al., 2002; Gheo ghe e al., 2007; Jin Im & Lee, 2015; Yao e al., 2015]. Addi ionally, hey ha e an ad an age o ease o syn hesis, low cos , lexible s e ic e ec s and suppo ing elec onic e ec s. P ope ies o hese molecules a e widely use ul in a b oad spec um o ields in physics o in chemis y as well as in biological sciences. F om hese we can men ion magne ism, luminescence, op ical p ope ies, selec i i y owa ds speci ic molecules, ca alysis and an imic obial ac i i y [C is ó ão e al., 2014; Jin Im & Lee, 2015; Yao e al., 2015]. 17 2.3 Coo dina ion Chemis y o Co(II) and Co(III) Up o now, he e a e almos 40 000 c ys al s uc u es con aining Co(II) o Co(III) ions in he Camb idge S uc u al Da abase (CSD; e sion 5.40, upda e Feb ua y 2019) [Allen e al., 1994]. Mo e han 25 000 o hem a e hexacoo dina ed, exhibi ing oc ahed al geome y, sligh ly dis o ed in he case o unequal ligands. The popula ion o ou - and i e-coo dina ed Co(II) ions is compa able (ca. 5 000 s uc u es each, up o now) and hese complexes exhibi e ahed al o squa e plana geome ies in he case o coo dina ion numbe 4; igonal-bipy amidal and he squa e py amidal geome ies in i e-coo dina ed complexes. When wo king wi h pa amagne ic Co(II) and diamagne ic Co(III) compounds, we should emembe he ollowing ac s abou he s abili y o such compounds and he oxida ion, which is an essen ial s o yline in he solu ion chemis y. The e a e wo pa icula aspec s in luencing he a ou able ou e o he eac ions. Co(III) exhibi s a s ong a ini y o ni ogen dono a oms and complexes o Co(III) a e kine ically ine [Co on e al., 1999; G eenwood & Ea nshaw, 1997]. E en only a change o he ligand can ha e an e ec on oxida ion- educ ion beha iou [Chambe s & Holliday, 1975]. Table 2.3.1 illus a es he ema kable sensi i i y o he educ ion po en ial o he Co(III)/Co(II) couple o di e en ligands. Thus, he p esence o some ligands such as salen ype Schi bases makes Co(II) uns able in an ai a mosphe e [G eenwood & Ea nshaw, 1997]. Table 2.3.1 E° o some Co(III)/Co(II) couples in acidic solu ion [G eenwood & Ea nshaw, 1997]. Couple E°/V [Co(H2O)6]3+ + e-  [Co(H2O)6]2+ 1.83 [Co(C2O4)3]3- + e-  [Co(C2O4)3]4- 0.57 [Co(ed a)]- + e-  [Co(ed a)]2- 0.37 [Co(bpy)3]3+ + e-  [Co(bpy)3]2+ 0.31 [Co(en)3]3+ + e-  [Co(en)3]2+ 0.18 [Co(NH3)6]3+ + e-  [Co(NH3)6]2+ 0.11 [Co(CN)6]3- + H2O + e-  [Co(CN)5(H2O)]3- + CN- -0.8 ½ O2 + 2 H+ + 2 e-  H2O 1.23 18 Wi h espec o he a o emen ioned ac s, he syn hesis o he complexes wi h Co(II) ion coo dina ed by a numbe o ni ogen dono a oms can be achie ed by he eac ion conduc ed unde non-oxida i e condi ions, such as an a gon a mosphe e. The o he possibili y o achie ing he Co(II) complex is o use s ic ly O-dono ligand. The coo dina ion chemis y o Co(III) is e y simple since he majo i y o i s complexes con ain he cen al a om wi h he coo dina ion numbe 6 and oc ahed al symme y, sub ly dis o ed i needed. As has al eady been poin ed ou , cobal (III) shows a pa icula a ini y o ni ogen and i s complexes a e kine ically ine and low-spin. Howe e , Co(III) complexes a e diamagne ic in gene al and hemsel es a e no sui able as magne ic unc ional ma e ials, he dicho omy be ween he ine ness o he wo oxida ion s a es has enabled he de elopmen o Co(III) hexacoo dina ed complexes as an icance o an i i al p od ugs. Co(III) complexes wi h neu al N-dono ligands unde go educ ion in biological sys ems o o m labile Co(II) complexes, which subsequen ly elease hei ligands as a cy o oxic payload. Fo example, complexes o he gene al s uc u al o mula [Co(SB)(L)2]+ (whe e SB = Schi base o he salen ype and L = a neu al N-dono ligand) exhibi ed ac i i y o A549 lung cance cells [King e al., 2019]. Te a- and pen a-coo dina ed Co(III) complexes a e gene ally less common han hose wi h hexacoo dina ion. Applica ions o such complexes we e in es iga ed in a ious ields, such as biological implica ions o ca alysis. As an example, a Co(III)/Co(II) based edox cycle in squa e-plana Co(III) complexes wi h py oleca boxamide ligands is used in ca alysis in ni o educ ion eac ions [Yaday e al., 2017], o se ies o squa e-py amidal salen ype Co(III) complexes we e es ed as ca alys s o he copolyme iza ion o cyclohexene oxide and CO2 [Cohen e al., 2006]. On he o he hand, Co(II) complexes display a la ge a ie y o coo dina ion en i onmen s; namely high-spin and low-spin oc ahed al, e ahed al, squa e and high- spin and low-spin i e-coo dina e complexes ( igonal-bipy amidal and squa e py amidal) as well as in e media e con igu a ions [Co on e al., 1999]. The in e es ing class o Co(II) complexes is {CoA2X2} – e ahed al dihalido Co(II) complexes wi h he e oa oma ic N,N-dono chela ing ligands possessing easy-plane magne ic aniso opy showing ield-induced slow magne ic elaxa ion [Smolko e al., 2015; Smolko e al., 2016]. The e a e also Co(II) complexes wi h coo dina ion numbe highe han 6 which 19 a e eached by using polyhap o o polyden a e ligands like cyclopen adiene, benzene o c own-e he s. 2.4 Coo dina ion Chemis y o Ni(II) The e a e mo e han 37 000 Ni(II) complexes in he CSD om he ecen e sion o Feb ua y 2019. The mos equen coo dina ion numbe s o Ni(II) complexes a e 6 (app ox. 18 000 hi s) and 4 wi h mo e han 15 000 s uc u ally cha ac e ized complexes. The o igin o he s able polyhed a o ansi ion me als lies in he localiza ion o ou e alence d o bi als which ha e di ec ional cha ac e . Hexacoo dina ed Ni(II) complexes ha e he p incipal s e eochemis y o an oc ahed on, sligh ly dis o ed when needed. The coo dina ion numbe 4 in Ni(II) complexes p oduces wo di e en geome ies, namely squa e-plana , e ahed al and complexes wi h in e media e geome ies be ween hese wo. Acco ding o c ys al ield heo y, squa e-plana coo dina ion complexes a e, o he han a ew pa icula examples, essen ially diamagne ic while hose o e ahed al geome y a e pa amagne ic. Oc ahed al Ni(II) complexes a e s udied in many ields, o ins ance hey a e good candida es o s udying he sign and magni ude o he ze o-field spli ing pa ame e D [I aniko á e al., 2006] o hei ca aly ic ac i i y is used o s imula e o ganic eac ions such as a yla ion and me hyla ion o allenamides [Liu e al., 2018] o syn hesis o indeno-py imidine de i a i es [Gangu e al., 2019]. Te ahed al Ni(II) complexes a e a e and usually achie ed by he selec ion o ligand se . Fo example, he use o an N,N'-ligand wi h he combina ion o halide ligands p oduces a e ahed al Ni(II) complex ac ing as a ca alys in which he coo dina ion si es occupied by halide ligands ep esen he ca aly ic cen es [Zhang e al., 2019]. On he o he hand, squa e-plana Ni(II) complexes a e mo e common and used as unc ional ma e ials in a ious a eas such as ca alysis [Foge on e al., 2019; Shen e al., 2018] o biological ac i i y [S eekuma e al., 2017; Biswas e al., 2018]. 2.5 Coo dina ion Chemis y o Ln(III) Fo unde s anding he coo dina ion chemis y o he -block, i is necessa y o cla i y he p ope ies o lan hanides as elemen s. The la ge, highly cha ged, Ln(III) ions a e ha d Lewis acids, and he e o e p e e o coo dina e ha d dono a oms such as oxygen and ni ogen. In con as , sulphu and phospho ous will be less a ou ed as dono a oms. Highly p e e ed coo dina ion o wa e molecules is an impo an ac o 20 caused by he high hyd a ion ene gy o he Ln(III) ion which means ha he syn heses o complexes wi h mono- and biden a e ligands o en need o be ca ied ou in nonpola sol en s, weakly coo dina ing o minimize compe i ion, such as CH3CN [Kal soyannis & Sco , 1999]. As a consequence o he la ge size o he lan hanide ions, high coo dina ion numbe s (up o 12) a e ound. An impo an ac is ha he -o bi als a e ʻinne ʼ o bi als, shielded om he e ec s o he su ounding anions and he e o e no able o pa icipa e in di ec ional bonding. The e a e none o he ligand- ield e ec s as in ansi ion me al chemis y wi h he p e e ence o oc ahed al o o he polyhed al coo dina ion. The coo dina ion numbe is, he e o e, dominan ly de e mined by s e ic equi emen s, i.e. how many ligands can be packed ound he cen al lan hanide ion [Co on, 2006]. As al eady no ed, o lan hanides, he e is no cha ac e is ic coo dina ion numbe as he e is in he case o ansi ion me als, coo dina ion numbe canno be deduced e en om he colou o he compound, no e en om he abso p ion spec um. The majo i y o Ln(III) ions a e colou less o he eye and ha e e y weak abso p ion spec a, no e y much in luenced by hei en i onmen . Single c ys al X- ay di ac ion s udies a e o en he only way o de e mining he coo dina ion polyhed on. Coo dina ion numbe s 3, 4, 5 and 6 in lan hanide complexes a e no e y common; his a angemen is ob ained by ligands wi h high second-o de s e ic e ec s. The mos equen coo dina ion numbe s a e 7, 8 and 9. The mos common geome ies encoun e ed wi h he se en-coo dina ion o Ln(III) ion a e capped oc ahed al and capped igonal p isma ic; se e al complexes adop pen agonal bipy amidal geome y. In he s uc u es o eigh -coo dina e Ln(III) ions, wo geome ies p edomina e – dodecahed al and squa e an ip isma ic, while he ene gy di e ence be ween hem is likely o be small. Less common, bu s ill occu ing is he cubic coo dina ion. Howe e , he ideal polyhed a a e a ely obse ed; mos o he eal geome ies a e de o med o ms o ideal polyhed a. T icapped igonal p isma ic is he mos amilia example o nine-coo dina e geome y. This polyhed al geome y is adop ed o he [Ln(H2O)9]3+ ions (Ln = Nd, Eu, Tb) which we e in es iga ed o a new phenomenon, namely cha ge ans e om he noncoo dina ed anions o he coo dina ed wa e molecules ia hyd ogen bonds [Nelyubina e al., 2014]. 27 [Ni2(o- an-en)2Mn(N3)2] CIBPAF e anuclea [Jia e al., 2007] [Ni(o- an-en)Na(H2O)(C2N3)] LORYOH dinuclea [Wang & Shen, 2009] [Ni(o- an-en)Na(ClO4)(MeOH)] NOQMEM dinuclea [Xiao, 2009] [Ni(o- an-en)Na(ClO4)]n VILXUL 1D [Bhowmik e al., 2013] [Ni2(o- an-en)2Na]BF4 VILYAS inuclea [Bhowmik e al., 2013] [Ni(o- an-en)Na(NO3)] VILYEW dinuclea [Bhowmik e al., 2013] {Ni(o- an-en) - 4 } complexes [Ni(o- an-en)Sm(NO3)3] ·CH3COCH3 ARIDEL01 dinuclea [Jin e al., 2011] [Ni(o- an-en)Eu(NO3)3] ·CH3COCH3 QAPXIQ dinuclea [Jin e al., 2011] [Ni(o- an-en)Tb(NO3)3] ·CH3COCH3 QAPXOW dinuclea [Jin e al., 2011] [Ni(o- an-en)Ce(NO3)2]NO3 MEFYAA inuclea [Güngö & Kose, 2017] [Ni(o- an-en)La(NO3)2(dp )] NOFLAX dinuclea [Ami khano e al., 2014] {Ni(o- an-en) - 4 - 3d/4d} complexes [Ni(o- an-en)Ho(H2O)4Co (CN)6]·3H2O BIKBAB inuclea [Dong e al., 2018] [Ni(o- an-en)Ho(H2O)4Fe (CN)6]·3H2O BIKBEF inuclea [Dong e al.;, 2018] [Ni4(o- an-en)4Tb4(H2O)14Mo2 (CN)16][Mo(CN)8]·21H2O KUNBUR clus e [Long e al., 2010] [Ni(o- an-en)Gd(H2O)4C (CN)6] ·MeOH·2H2O QUXWAJ inuclea [Chen e al., 2015] [Ni(o- an-en)Tb(H2O)4C (CN)6] ·MeOH·2H2O QUXWEN inuclea [Chen e al., 2015] [Ni(o- an-en)Tb(H2O)4Fe(CN)6] ·MeOH·2H2O QUXWIR inuclea [Chen e al., 2015] [Ni(o- an-en)Gd(H2O)4Fe(CN)6] ·MeOH·2H2O QUXWOX inuclea [Chen e al., 2015] 28 2.7 Coo dina ion Chemis y o he Benzoa o Ligand Benzoic acid, HBz, C6H5COOH is a colou less compound, solid a oom empe a u e. I possesses good solubili y in alcohols, e he and benzene, lowe in wa e . I s solubili y in wa e a oom empe a u e is only 0.29 g / 100 ml [H nčia , 1982]. Benzoic acid has a mel ing poin o 122.3 °C. This excep ionally high alue is a consequence o i s compac c ys al s uc u e. I c ys allizes as anhyd ous and i s c ys al s uc u e con ains wo molecules o ming dime ic uni s in which he indi idual molecules a e linked by a pai o O-H···O hyd ogen bonds (HBs) be ween wo ca boxylic g oups (Fig. 2.7.1) [B uno & Randaccio, 1980]. Figu e 2.7.1 Dime ic sup amolecula s uc u e o HBz; ed: oxygen, g ey: ca bon, whi e hyd ogen a oms [B uno & Randaccio, 1980]. A e i s dep o ona ion, benzoic acid o ms he benzoa e ligand C6H5COO-, Bz which is widely used in coo dina ion chemis y as an O-dono ligand. A sea ch in he CSD shows mo e han 2 700 published c ys al s uc u es con aining benzoa e in any o m. Benzoa e ligand can dona e up o eigh elec ons o he cen al a om/s which leads o a ich a ie y o coo dina ion modes (Scheme 2.7.1). Scheme 2.7.1 Possible modes o coo dina ion o Bz ligand. 29 In ega d o he p e iously men ioned ac s abou he s abili y o Co(II)/Co(III) complexes depending on he dono a om selec ion, he syn hesis o he complexes wi h Co(II) ion can be achie ed by using s ic ly O-dono ligands. The las upda e o CSD gi es 124 complexes wi h Bz ligand coo dina ed o Co a oms, 105 o hem con ain he me al ion in oxida ion s a e II. Addi ionally, ou p e ious wo k wi h he {NiIIBz} sys em sugges s he possibili y o simila beha iou o Co and his in u n opens he possibili y o examina ion o Co(II) in molecula magne ism [V áblo á e al., 2016]. 30 3 Aims o hesis The aim o he ensuing disse a ion is o p epa e and s udy a se ies o no el Ni(II), Co(II) and lan hanide compounds as well as bime allic 3d-4 complexes using N,O- and/o O-dono ligands. The goal is o design and subsequen ly imp o e syn he ic p ocedu es leading o he p epa a ion o desi able p oduc s which will be chemically, spec oscopically and c ys allog aphically s udied. Magne ic s udy o selec ed complexes will be ca ied ou in he inal phase. To achie e his pu pose, he ollowing pa ial goals we e es ablished: 1. Recen e iew o heo e ical backg ound and li e a u e will be ca ied ou using mode n c ys allog aphic and bibliog aphic da abases. The e iew will be ocused on he p epa a ion, c ys al s uc u e and p ope ies o known Ni(II), Co(II), Gd(III), Ce(III) and Dy(III) complexes as well as hei bime allic 3d-4 combina ions. Special emphasis will be placed on he selec ion o ligands, mainly Schi base and ca boxyla o ligands. 2. Acco ding o p e ious heo e ical esea ch, he p ope syn he ic p ocedu es will be designed and ca ied ou in an e o o p epa e and isola e no el 3d, 4 and 3d-4 compounds. The aim is o p epa e a ich a ie y o geome ies o molecula species which leads o di e en p ope ies, especially magne ic, o he esul ing compounds. The p epa a ion o single c ys als is highly p e e ed. A con enien Schi base ligand will be syn hesized, isola ed and used as a s a ing ma e ial o syn heses wi h me al ions. 3. The p epa a ion and isola ion o a la ge numbe o new compounds is assumed. The inal p oduc s as well as side ones will be chemically (elemen al analysis) and spec oscopically (IR, UV-VIS) cha ac e ized and hei c ys al and molecula s uc u es will be de e mined using X- ay s uc u e analysis. The combina ion o all a ailable echniques will be used o de e mine he exac geome y o molecula species and asce ain he pu i y o inal samples. 4. In he case o selec ed compounds hei magne ic p ope ies will be s udied. The obse ed magne ic p ope ies will be co ela ed wi h known c ys al s uc u es o he s udied complexes. 5. The expe imen al esul s ob ained will be published in he scien i ic jou nals, pos e s o lec u es a scien i ic e en s such as con e ences, mee ings e c. 31 4 Expe imen al sec ion 4.1 Ma e ials Benzoic acid, e hylenediamine, o- anillin, CoCO3, Co(OH)2, NiCl2, NiCO3, Gd(NO3)3·6H2O, GdCl3·6H2O, CeCl3·7H2O, DyCl3·6H2O and sol en s e hanol, me hanol, isop opanol, ace oni ile and die hyle he , all o analy ical g ade we e pu chased om comme cial sou ces and used as ecei ed. 4.2 Syn heses 4.2.1 Syn hesis o Schi base as N,O-dono ligand H2(o- an-en) (1) Fo he syn hesis o H2(o- an-en) a modi ied me hod o ha al eady epo ed [Ghose, 1984] was used. E hylenediamine (0.1 ml, 1.5 mmol) was added o 50 ml o e hanolic solu ion o o- anillin (0.4542 g, 3 mmol). The mix u e was placed in a boiling lask and e luxed o 5 hou s. The inal solu ion was il e ed and le o c ys alliza ion. A e ew hou s, da k yellow c ys als o ou p oduc appea ed. The c ude p oduc was il e ed, washed wi h 2 ml o die hyle he . Yield: 90 %. Anal. (%), calcula ed o C18H20O4N2 (M = 328.36 g.mol−1):C, 65.83; H, 6.15; N, 8.53; ound: C, 66.30; H, 6.33; N, 8.57. FT-IR (cm-1): 3746w, 2997w, 2931w, 2848w, 1631s, 1463s, 1438m, 1408m, 1325w, 1295w, 1246 s, 1189m, 1170m, 1133m, 1080s, 1054m, 1010m, 987m, 962s, 836s, 791s, 782s, 740s, 729s, 620m, 521m, 441m. UV-Vis (nm) in E OH: 219, 264; in CHCl3: 265, 334. 1H-NMR (ppm): 3.92m, 6.84m, 7.267s, 8.323s, 13.5s,b. 13C-NMR (ppm): 56.056, 59.467, 114.084, 118.032, 118.419, 123.149, 148.269, 151.402, 166.643. 32 4.2.2 {T – (o- an-en)} complexes as p ecu so s o 3d-4 complexes [Ni(o- an-en)]·nH2O (4) Solid H2(o- an-en) (2 g, 6 mmol) and nickel(II) ca bona e (0.7 g, 6 mmol) we e placed in 100 ml o wa e and hea ed in an open beake . A e one hou o eac ion he esul ing b own mic oc ys alline p oduc was sepa a ed by il a ion, washed wi h 2 ml o e hanol and d ied in ai . Single c ys als sui able o X- ay da a collec ion we e ob ained by dissol ing o he mic oc ys alline p oduc in ace one; om he esul ing clea b own-yellow solu ion he ga ne ed c ys alline p oduc 4 p ecipi a ed o e nigh . Anal. (%), calcula ed o C18H20O5N2Ni ([Ni(o- an-en)]·nH2O, n = 1; M = 403.05 g.mol−1): C, 53.64; H, 5.00; N, 6.95; ound: C, 52.14; H, 4.79; N, 6.54. FT-IR (cm-1): 3454b, 3055w, 2934w, 2835w, 1621s, 1602s, 1547m, 1472s, 1447s, 1392w, 1314s, 1232s, 1167m, 1109m, 1092m, 1080m, 1001m, 973m, 860m, 777w, 722s, 662w, 619m, 571w, 543w, 480m, 426m, 401m. [Ni(o- an-en)]·H2O·E OH (5) Single c ys als o complex 5 we e ob ained by he same p ocedu e as was used o complex 4, wi h he di e ence ha he c ude p oduc was ec ys allized om e hanol. A e dissol ing he c ude p oduc a clea b own-yellow solu ion was ob ained which yielded o e nigh ed p isms o 5 exhibi ing low s abili y upon s anding in ai . FT-IR (cm-1): 3446b, 3055w, 2934w, 2834w, 1621s, 1602s, 1547m, 1471s, 1447s, 1392w, 1313s, 1232s, 1167m, 1109m, 1079s, 1000m, 973m, 859m, 777w, 722s, 667w, 619m, 571w, 542w, 480m, 425m, 401s. [Ni(o- an-en)]·H2O·iP OH (6) Single c ys als o complex 6 we e ob ained by he same p ocedu e as was used o complex 4, wi h he di e ence ha he c ude p oduc was ec ys allized om isop opanol. Single c ys als o 6, in he o m o b own iny needles, sepa a ed o e nigh , we e il e ed, quickly washed wi h a small po ion o cold isop opanol and d ied in ai . Anal. (%), calcula ed o C21H28O6N2Ni (M = 463.15 g.mol−1): C, 54.46; H, 6.09; N, 6.05; ound: C, 52.04; H, 5.13; N, 6.59. FT-IR (cm-1): 3508w, 3478w, 3330w, 3056w, 2961w, 2937w, 2840w, 1621s, 1603s, 1548m, 1473s, 1449s, 1408m, 1335w, 1314s, 1243s, 1232s, 1168m, 1136w, 1108m, 33 1080s, 1000m, 972m, 958m, 893w, 858m, 820w, 782w, 727s, 660w, 620m, 572w, 542w, 480m, 463w, 425m, 400s. [CoII(o- an-en)(H2O)] (7) Solid Co(OH)2 (0.07 g, 0.76 mmol) was added o a deoxygena ed wa e suspension o H2(o- an-en) (0.25 g, 0.76 mmol, 35 ml) a oom empe a u e unde an ine a gon a mosphe e. An o ange solid appea ed a e a ew minu es o s i ing. The mix u e was s i ed o e nigh and he inal da k o ange mic oc ys alline p oduc 7 was il e ed, washed wi h wa e and d ied in ai . Yield based on Co: 80 %. Anal. (%), calcula ed o CoC18H20N2O5 (M = 403.29 g.mol−1): C, 53.61; H, 5.00; N, 6.95; ound: C, 53.80; H, 4.88; N, 6.87. FT-IR (cm-1): 3315b, 3055w, 2899w, 2827w, 1651m, 1625m, 1600m, 1545m, 1468m, 1438s, 1391m, 1310m, 1239s, 1213s, 1169m, 1078m, 980m, 967m, 853m, 743m, 723s, 640m, 421m. [CoIII2(o- an-en)3]·4MeCN, Fo m I (8) The mic oc ys alline p oduc 7 was dissol ed in ace oni ile in ai wi h s i ing a oom empe a u e and a e dissolu ion was le aside o c ys alliza ion. Wi hin a ew hou s he esul ing solu ion had changed colou om da k ed o b own-black. Black block c ys als o 8 we e ob ained a e a ew days. As he c ys als we e uns able when sepa a ed om he mo he liquo , p esumably due o loss o sol en molecules, hey we e moun ed o di ac ion da a collec ion immedia ely a e emo ing om he mo he liquo . [CoIII2(o- an-en)3]·4MeCN, Fo m II (9) Solid Co(OH)2 (0.07 g, 0.76 mmol) was added o a wa e suspension o H2(o- an-en) (0.25 g, 0.76 mmol, 20 ml) a oom empe a u e in ai and s i ed o e nigh un il he mic oc ys alline solid had changed colou om yellow-b own o black. The p oduc hus o med was il e ed, d ied in ai and ec ys allized om ho ace oni ile solu ion (~60 - 70 C). Black block c ys als o 9 appea ed a e a ew days. The c ys als o 9 we e no s able in ai , so hey we e moun ed o di ac ion da a collec ion immedia ely a e emo ing om ace oni ile solu ion. 34 [CoIII(o- an-en)(H2O)Cl] (10) The p e iously p epa ed solid o [CoIIL(H2O)] (7, 0.0217 g, 0.054 mmol) was added o an e hanol solu ion o GdCl3 (0.02 g o GdCl3·6H2O, 0.054 mmol). The o ange solu ion u ned o da k b own (almos black) in a ew seconds. The solu ion was il e ed and le o c ys alliza ion a ambien condi ions. A e a ew days, a ew da k ed- b own c ys als sui able o X- ay di ac ion analysis appea ed. [CoIII(o- an-en)(H2O)Cl]·2MeCN (11) Solid GdCl3·6H2O and he p e iously p epa ed [CoII(o- an-en)(H2O)] (7) in mola a io 1 : 1 we e bo h dissol ed in ace oni ile a mild condi ions. Single c ys als o 11 we e collec ed om mo he liquo a e se e al days. Un o una ely, de ails o he syn hesis we e los in he lab no ebook des oyed in a i e in he chemis y building o P. J. Ša á ik Uni e si y in Košice. 4.2.3 Syn heses o {T – (o- an-en) – Ln} complexes [Ni(o- an-en)Gd(NO3)3]∙2MeCN (12) Solid H2(o- an-en) (1), Ni(NO3)2·6H2O and Gd(NO3)3·6H2O in mola a io 1 : 1 : 1 we e dissol ed in ace oni ile unde mild condi ions. Single c ys als o 12 we e collec ed om mo he liquo a e se e al days. Un o una ely, de ails o he syn hesis we e los in he lab no ebook des oyed in a i e in he chemis y building o P. J. Ša á ik Uni e si y in Košice. C ys als we e no s able due o loss o CH3CN and he e o e, he di ac ion da a we e collec ed using he single c ys al moun ed on a MiTeGen suppo (Mic oMoun ™) immedia ely a e emo ing om mo he liquo . [Ni(o- an-en)CeCl3(H2O)] (13) Solid H2(o- an-en) (2 g, 6 mmml) and nickel(II) ca bona e (0.7 g, 6 mmol) we e placed in 100 ml o wa e and hea ed in an open beake . A e one hou o eac ion he esul ing b own mic oc ys alline p oduc (c ude nickel complex o 4) was sepa a ed by il a ion, washed wi h 2 ml o e hanol and d ied in ai . The d y p oduc was used in he nex s ep o he syn hesis wi hou u he pu i ica ion. Solid CeCl37H2O (0.3 g, 0.8 mmol) was dissol ed in 10 ml o e hanol and he esul ing clea solu ion was added o he b own e hanolic solu ion o 4 (50 ml o e hanol). A e 15 minu es o s i ing, he esul ing o ange mic oc ys alline complex o 13 was sepa a ed by il a ion and washed h ee imes wi h 2 ml o e hanol. Single c ys als o 13 we e ob ained by ec ys alliza ion 35 o he mic oc ys alline complex using oom empe a u e di usion o he MeOH solu ion in o iP OH. Yield: 81 %. Anal. (%), calcula ed o CeNiC18H20Cl3O5N2 (M = 649.53 g.mol−1): C, 33.28; H, 3.10; N, 4.31; ound: C, 32.50; H, 3.39; N, 4.30. FT-IR (cm-1): 3334wm, 3248m, 2952w, 2926w, 1638m, 1622s, 1608s, 1560m, 1459s, 1431m, 1410w, 1390w, 1342w, 1324w, 1291s, 1243s, 1230s, 1198m, 1165m, 1139w, 1101w, 1077s, 1053m, 989m, 980m, 956s, 900m, 864m, 847m, 783s, 739 s, 686m, 667w, 626m, 579m, 549m, 536m, 494m, 440s, 408s. [Ni(o- an-en)GdCl3(H2O)] (14) Fo he syn hesis o 14, he same p ocedu e was used as o he Gd(III) complex wi h he modi ica ion ha GdCl3·6H2O (0.3 g, 0.8 mmol) was used ins ead o CeCl37H2O. Single c ys als sui able o X- ay analysis we e ob ained by ec ys alliza ion using di usion o a MeOH solu ion o GdCl3 in o an iP OH solu ion o [Ni(o- an-en)] a oom empe a u e. Yield: 65 %. Anal. (%), calcula ed o GdNiC18H20Cl3O5N2 (M = 666.66 g.mol−1): C, 32.43; H, 3.02; N, 4.20; ound: C, 31.82; H, 2.73; N, 4.23. FT-IR (cm-1): 3347wm, 3242m, 2949w, 2927w, 1622s, 1609s, 1560m, 1471s, 1462s, 1435m, 1409m, 1390w, 1340w, 1323w, 1295s, 1247s, 1230s, 1198m, 1166m, 1142w, 1100w, 1077s, 1053m, 988m, 980m, 957s, 902m, 866m, 845m, 783s, 739 s, 692m, 669w, 629m, 580m, 550m, 539m, 497m, 442m, 409s. [Ni(o- an-en)DyCl3(H2O)] Fo m I (15) Fo he syn hesis o 15, he same p ocedu e was used as o he Ce(III) complex wi h he modi ica ion ha DyCl3.6H2O (0.3 g, 0.8 mmol) was used ins ead o CeCl37H2O. C ys als o 15 we e ob ained by ec ys alliza ion using di usion o a me hanolic solu ion o he mic oc ys alline p oduc in o iP OH wi h a empe a u e g adien om 70 °C a he bo om o he beake o oom empe a u e a he op o solu ion. Yield: 70 %. Anal. (%), calcula ed o DyNiC18H20Cl3O5N2 (M = 671.91 g.mol−1): C, 32.18; H, 3.00; N, 4.17; ound: C, 31.36; H, 3.23; N, 4.00. 36 FT-IR (cm-1): 3342wm, 3242m, 2949w, 2928w, 1623s, 1610s, 1560m, 1462s, 1436m, 1400m, 1389w, 1340w, 1323w, 1294s, 1248s, 1229s, 1197m, 1166m, 1077s, 1053m, 988m, 978m, 958s, 903w, 866m, 788s, 739 s, 693m, 669w, 630m, 580m, 550m, 497m, 443m, 409s. [Ni2Ce2(o- an-en)2Cl6] (16) A p e iously p epa ed solid o [Ni(o- an-en)CeCl3(H2O)] (13) was dissol ed in e hanol. A closed lask wi h a e y dilu e solu ion was kep in he o en a 80 °C o 3 days. The o en was allowed o cool o oom empe a u e o e a pe iod o 13 hou s and he lask was opened. Red-o ange hombic c ys als we e il e ed and washed wi h cold e hanol. FT-IR (cm-1): 2936w, 2840w, 1628s, 1606s, 1560m, 1470s, 1453s, 1431s, 1410m, 1389m, 1335w, 1319m, 1289s, 1231s, 1176m, 1104m, 1076s, 990m, 960s, 859m, 801s, 771m, 751m, 730s, 681s, 666m, 625m, 604w, 588w, 575m, 542m, 492m, 473m, 439s. [Ni(o- an-en)DyCl3] (17) A p e iously p epa ed solid o [NiLDyCl3(H2O)] (15) was dissol ed in e hanol. A closed lask wi h a e y dilu e solu ion was kep in he o en a 80 °C o 3 days. The o en was allowed o cool o oom empe a u e o e a pe iod o 13 hou s and he lask was opened. A ew agile small o ange c ys als we e collec ed manually and s udied by single c ys al X- ay di ac ion. [Ni(o- an-en)DyCl3]·E OH (18) A p e iously p epa ed solid o [NiLDyCl3(H2O)] (15) was dissol ed in e hanol and laye ed wi h isop opanol a oom empe a u e. A e se e al hou s o ange- ed c ys als o 18 in he o m o needles, sui able o X- ay di ac ion analysis, we e collec ed. [Ni(o- an-en)DyCl3(H2O)] Fo m II (19) A p e iously p epa ed solid o [Ni(o- an-en)DyCl3(H2O)] (15) was dissol ed in e hanol and a laye o isop opanol was ca e ully added and he lask was closed. A e di usion inished, he beake was opened and pu on a me allic su ace held a 70°C. A e se e al hou s, ed-o ange hombic c ys als we e il e ed and washed wi h cold isop opanol. 43 Table 4.3.1. Con inued. 10 11 12 Empi ical o mula C18H20ClCoN2NiO5 C22H26ClCoN4O5 C22H24GdN7NiO13 Fo mula weigh [g.mol-1] 438.74 520.85 810.44 C ys al sys em, space g oup o ho hombic, Pbca monoclinic, P21/n o ho hombic, Pna21 Uni cell dimensions [Å, °, Å3] a = 13.8127 (5) b = 15.0784 (7) c = 17.1178 (5) α = 90 β = 90 γ = 90 V = 3565.2 (2) a = 13.3890 (9) b = 11.0995 (5) c = 16.0031 (10) α = 90 β = 101.805 (7) γ = 90 V = 2327.9 (2) a = 28.3598 (17) b = 11. 1664 (4) c = 9.40200 (4) α = 90 β = 90 γ = 90 V = 2856.4 (2) Z 8 4 4 Calcula ed densi y [Mg.m-3] 1.635 1.486 1.885 Abs. coe . [mm-1] 1.146 0.893 3.038 C ys al o m, colou , size [mm] da k ed-b own block 0.106 x 0.080 x 0.052 dich oic da k o ange/black block 0.205 x 0.110 x 0.018 yellow-o ange pla e 0.285 x 0.131 x 0.028 Tempe a u e [K] 300 (2) 100 (2) 100 (2) Radia ion [Å] MoKα (  = 0.71073) MoKα (  = 0.71073) MoKα (  = 0.71073) Di ac ome e XCalibu , CCD de ec o XCalibu , CCD de ec o XCalibu , CCD de ec o θ ange o da a collec ion [°] 2.800 - 25.496 3.301 - 25.992 3. 239 - 25.497 Index anges -16 ≤ h ≤ 16, -18 ≤ k ≤ 12, -19 ≤ l ≤ 20 -16 ≤ h ≤ 15, -13 ≤ k ≤ 13, -19 ≤ l ≤ 19 -34 ≤ h ≤ 34, -13 ≤ k ≤ 14, -10 ≤ l ≤ 10 Re l. coll. / indp. 10813 / 3323 17719 / 4565 16034 / 4960 GooF (S) 1.026 0.999 1.066 Final R indices [I > 2(I)] R1 = 0.0452, wR2 = 0.0778 R1 = 0.0629, wR2 = 0.1351 R1 = 0.0411, wR2 = 0.1043 R indices (all da a) R1 = 0.0898, wR2 = 0.1021 R1 = 0.0953, wR2 = 0.1558 R1 = 0.0508, wR2 = 0.1152 La ges di . peak and hole [e.Å-3] -0.331 ≤   ≤ 0.358 -0.792 ≤   ≤ 1.129 -1.068 ≤   ≤ 1.255 44 Table 4.3.1. Con inued. 13 14 15 Empi ical o mula C18H20Cl3CeN2NiO5 C18H20Cl3GdN2NiO5 C18H20Cl3DyN2NiO5 Fo mula weigh [g.mol-1] 649.54 666.67 671.92 C ys al sys em, space g oup monoclinic, P21/n monoclinic, P21/n monoclinic, P21/n Uni cell dimensions [Å, °, Å3] a = 7.1269 (3) b = 14.4698 (6) c = 21.0732 (12) α = 90 β = 93.014 (4) γ = 90 V = 2170.18 (18) a = 7.0236 (3) b = 14.3753 (9) c = 20.9662 (13) α = 90 β = 92.216 (5) γ = 90 V = 2115.3 (2) a = 7.00940 (10) b = 14.3916 (3) c = 20.9556 (5) α = 90 β = 91.833 (2) γ = 90 V = 2112.85 (7) Z 4 4 4 Calcula ed densi y [Mg.m-3] 1.988 2.093 2.112 Abs. coe . [mm-1] 3.341 4.411 4.813 C ys al o m, colou , size [mm] dich oic ed- o ange/colou less block 0.091 x 0.057 x 0.018 pale pink block 0.175 x 0.079 x 0.034 dich oic ed/colou less p ism 0.08 x 0.04 x 0.02 Tempe a u e [K] 299 (2) 295 (2) 293 (2) Radia ion [Å] MoKα (  = 0.71073) MoKα (  = 0.71073) MoKα (  = 0.71073) Di ac ome e XCalibu , CCD de ec o XCalibu , CCD de ec o XCalibu , CCD de ec o θ ange o da a collec ion [°] 3.653 - 28.384 3.230 - 24.997 2. 831 - 30.302 Index anges -9 ≤ h ≤ 9, -19 ≤ k ≤ 19, -28 ≤ l ≤ 26 -8 ≤ h ≤ 8, -10 ≤ k ≤ 17, -24 ≤ l ≤ 23 -9 ≤ h ≤ 8, -20 ≤ k ≤ 19, -29 ≤ l ≤ 28 Re l. coll. / indp. 6159 / 6159 9912 / 3716 26349 / 5820 GooF (S) 0.972 0.943 1.038 Final R indices [I > 2(I)] R1 = 0.0370, wR2 = 0.0990 R1 = 0.0589, wR2 = 0.0692 R1 = 0.0338, wR2 = 0.0587 R indices (all da a) R1 = 0.0642, wR2 = 0.1051 R1 = 0.1320, wR2 = 0.0864 R1 = 0.0577, wR2 = 0.0671 La ges di . peak and hole [e.Å-3] -0.640 ≤   ≤ 0.708 -1.148 ≤   ≤ 1.613 -0.821 ≤   ≤ 0.677 45 Table 4.3.1. Con inued. 16 17 18 Empi ical o mula C18H18CeCl3N2NiO4 C18H18Cl3DyN2NiO4 C20H24Cl3DyN2NiO5 Fo mula weigh [g.mol-1] 631.52 653.90 699.97 C ys al sys em, space g oup iclinic, P-1 iclinic, P-1 monoclinic, P21/c Uni cell dimensions [Å, °, Å3] a = 9.5527 (3) b = 11.0298 (3) c = 11.4447 (3) α = 69.564 (3) β = 82.214 (3) γ = 66.225 (3) V = 1034.06 (6) a = 8.1516 (9) b = 10.1225 (5) c = 12.7149 (11) α = 81.526 (6) β = 84.239 (8) γ = 76.196 (7) V = 1005.41 (15) a = 11.4426 (3) b = 8. 8478 (2) c = 23.5430 (4) α = 90 β = 96.376 (2) γ = 90 V = 2368.79 (9) Z 2 2 4 Calcula ed densi y [Mg.m-3] 2.028 2.160 1.963 Abs. coe . [mm-1] 3.499 5.051 4.298 C ys al o m, colou , size [mm] ed-o ange-b own block 0.165 x 0.094 x 0.031 pale b own-o ange sla 0.071 x 0.040 x 0.009 ed-o ange needle 0.586 x 0.095 x 0.084 Tempe a u e [K] 299 (2) 100 (2) 173 (2) Radia ion [Å] MoKα (  = 0.71073) MoKα (  = 0.71073) MoKα (  = 0.71073) Di ac ome e XCalibu , CCD de ec o XCalibu , CCD de ec o XCalibu , CCD de ec o θ ange o da a collec ion [°] 2.484 - 30.139 2.579 - 27.800 2. 887 - 30.053 Index anges -1 3≤ h ≤ 13, -15 ≤ k ≤ 14, -16 ≤ l ≤ 15 -10 ≤ h ≤ 10, -12 ≤ k ≤ 13, -16 ≤ l ≤ 14 -16 ≤ h ≤ 16, -11 ≤ k ≤ 12, -32 ≤ l ≤ 32 Re l. coll. / indp. 20870 / 5626 10592 / 4082 38460 / 6535 GooF (S) 1.143 1.036 1.072 Final R indices [I > 2(I)] R1 = 0.0303, wR2 = 0.0722 R1 = 0.0500, wR2 = 0.0899 R1 = 0.0231, wR2 = 0.0522 R indices (all da a) R1 = 0.0406, wR2 = 0.0863 R1 = 0.0965, wR2 = 0.1077 R1 = 0.0289, wR2 = 0.0546 La ges di . peak and hole [e.Å-3] -0.826 ≤   ≤ 0.929 -1.653 ≤   ≤ 0.850 -0.699 ≤   ≤ 1.225 46 Table 4.3.1. Con inued. 19 20 21 Empi ical o mula C18H20Cl3DyN2NiO5 C18H18Cl3DyN2NiO4 C14H16CoO7 Fo mula weigh [g.mol-1] 671.92 653.90 355.20 C ys al sys em, space g oup monoclinic, P21/n monoclinic, P21/n monoclinic, I2/a Uni cell dimensions [Å, °, Å3] a = 13.5202 (3) b = 9.4039 (2) c = 17.2556 (3) α = 90 β = 91.0114 (19) γ = 90 V = 2193.57 (8) a = 12.118 (3) b = 9.3732 (9) c = 18.545 (3) α = 90 β = 88.535(16) γ = 90 V = 2105.7 (6) a = 6.2299 (4) b = 34.115 (3) c = 6.9101 (4) α = 90 β = 95.689 (7) γ = 90 V = 1461.38 (17) Z 4 4 4 Calcula ed densi y [Mg.m-3] 2.035 2.063 1.614 Abs. coe . [mm-1] 4.636 4.823 1.207 C ys al o m, colou , size [mm] o ange needle 0.249 x 0.068 x 0.057 pale o ange sla 0.336 x 0.088 x 0.010 pale pla e 0.134 x 0.084 x 0.043 Tempe a u e [K] 301 (2) 173 (2) 293 (2) Radia ion [Å] MoKα (  = 0.71073) MoKα (  = 0.71073) MoKα (  = 0.71073) Di ac ome e XCalibu , CCD de ec o XCalibu , CCD de ec o XCalibu , CCD de ec o θ ange o da a collec ion [°] 2.880 - 30.362 2.748 - 28.046 4.204 - 26.487 Index anges -18 ≤ h ≤ 18, -13 ≤ k ≤ 12, -24 ≤ l ≤ 23 -14 ≤ h ≤ 15, -11 ≤ k ≤ 11, -14 ≤ l ≤ 24 -7 ≤ h ≤ 7, -42 ≤ k ≤ 42, -8 ≤ l ≤ 8 Re l. coll. / indp. 18511 / 5946 8808 / 4228 4564 / 1513 GooF (S) 1.018 1.048 1.175 Final R indices [I > 2(I)] R1 = 0.0299, wR2 = 0.0546 R1 = 0.0953, wR2 = 0.1426 R1 = 0.0397, wR2 = 0.0962 R indices (all da a) R1 = 0.0446, wR2 = 0.0600 R1 = 0.1893, wR2 = 0.1760 R1 = 0.0566, wR2 = 0.1323 La ges di . peak and hole [e.Å-3] -0.704 ≤   ≤ 0.519 -0.998 ≤   ≤ 2.450 -0.813 ≤   ≤ 1.049 47 5 Resul s and discussion 5.1 Schi base ligand (o- an-en)2- as N,O-dono ligand Schi base H2(o- an-en) was p epa ed by he eac ion o e hylenediamine and o- anillin in a 1:2 mola a io. The p epa a ion and he basic cha ac e iza ion we e al eady desc ibed by Ghose [1983; 1984] and i s c ys al s uc u e was published by Cunningham e al. [2004] (cis isome ) and Co eia e al. [2005] ( ans isome ); see Sec ion 2.6 in he heo e ical backg ound o his wo k. By modi ying he eac ion condi ions, he Schi eac ion was ca ied ou in e hanol unde e lux condi ions while p oducing wa e as a side p oduc (Scheme 5.1.1). Scheme 5.1.1 The Schi eac ion o e hylenediamine and o- anillin in a 1:2 mola a io. The p oduc 1 was p epa ed in mic oc ys alline o m by il a ion om a ho solu ion. The iden i ica ion and he pu i y o he p oduc we e con i med by a ious echniques, including 1H-NMR, 13C-NMR, IR, UV-Vis spec oscopies and elemen al analysis. The c ys alline o m was p oduced by slow e apo a ion o he mo he liquo a e se e al hou s. The needle like yellow single c ys als we e cha ac e ized by single- c ys al X- ay analysis. The Schi base H2(o- an-en) (1) p epa ed by us c ys allizes in he non- cen osymme ic monoclinic space g oup Pc. The molecula s uc u e o he cis s e eoisome is suppo ed by in amolecula hyd ogen bonds be ween N a oms o he imine g oups, ac ing as accep o s, wi h hyd oxo g oups as dono s (Fig. 5.1.1a); Tab. 5.1.1). Addi ionally, i s c ys al s uc u e displays wo weake in e molecula hyd ogen bonds coming om a oma ic C5 and imine C11 dono a oms o ming he 3D packing in 1 (Fig. 5.1.1b); Tab. 5.1.1). 48 a) b) Figu e 5.1.1 a) The molecula s uc u e o 1. The he mal ellipsoids a e d awn a he 50 % p obabili y le el. In amolecula hyd ogen bonds a e d awn as o ange dashed lines. b) C ys al s uc u e o 1. In e molecula hyd ogen bonds a e d awn as o ange dashed lines. The ac plane is shown. Table 5.1.1 Po en ial hyd ogen bonds in 1. D–H···A D–H [Å] H···A [Å] D···A [Å] D–H···A [°] O2–H2O···N1 0.84 1.86 2.605 (3) 146 O3–H3O···N2 0.84 1.82 2.561 (3) 147 C5–H5···O3i 0.95 2.47 3.255 (3) 140 C11–H11···O2ii 0.95 2.47 3.404 (3) 168 Symme y codes: i: –1 + x, 1 + y, z; ii: x, 2 – y, 1/2 + z. 49 5.2 {T – (o- an-en)} complexes as p ecu so s o 3d-4 complexes In an a emp o syn hesize bime allic complexes, ou i s syn he ic expe imen s in he labo a o y included he in si u app oach. We conduc ed se e al expe imen s using nickel(II), cobal (II) and lan hanide(III) sal s combined wi h ou compa men al ligand H2(o- an-en) unde mild condi ions. O hem, wo can be men ioned in mo e de ail. Fi s ly, nickel(II) chlo ide, ce ium(III) chlo ide and he Schi base ligand H2(o- an-en) we e pu oge he in e hanol and he solu ion was e luxed o an hou . The inal solid p oduc was il e ed ou immedia ely and he il a e was le o c ys alliza ion a oom empe a u e. The majo p oduc was cha ac e ized as [Ni(o- an- en)CeCl3(H2O)]. This p oduc was p epa ed wi h highe pu i y and yield using a modi ied syn he ic p ocedu e and i will be analysed (compound 14) la e in Sec ion 5.4 o his wo k. A e a ew hou s, pale yellow p isma ic c ys als o 2 we e collec ed om he il a e, sui able o single-c ys al X- ay analysis. C ys alline p oduc 2 men ioned abo e was cha ac e ized as e hylenediammonium chlo ide and i s o ma ion can be explained as he esul o he decomposi ion o he Schi base H2(o- an-en) in acidic medium. Fu he analysis o he p ocesses in he eac ion sys em lead o he hypo hesis ha he acidic medium is o med a e he dep o ona ion o he ligand ( eleasing he wo p o ons) and he coo dina ion o he nickel cen al a om ( eleasing wo chlo ide anions om he nickel(II) chlo ide). E hylenediammonium chlo ide (2) c ys allizes in space g oup P21/c whe e only hal o he e hylenediammonium ca ion and one chlo ide ion o m he asymme ic uni . The es o he o mula is gene a ed h ough he cen e o symme y [1 – x, 1 – y, 1 – z] (Fig. 5.2.1a). Ca ions and anions a e held oge he by h ee hyd ogen bonds o he N–H···Cl ype gene a ing he hyd ogen bonding sys em o ming a 2D laye ed c ys al s uc u e pa allel o he bc plane (Fig. 5.2.1b); Tab. 5.2.1). We no e ha he c ys al s uc u e o e hylenediammonium chlo ide was al eady epo ed by se e al esea ch g oups [Ashida & Hi okawa, 1963; Reu e & Kas ne , 1997; Bujak e al., 2000; Kooijman e al., 2006; Dickman, 2007; Seidel, 2009; Gab o e al., 2009; Liu e al., 2010; Kubicki, 2009]. Consequen ly, he esul s o ou s uc u e analysis we e deposi ed as a CSD communica ion [V áblo á e al., 2017]. 50 a) b) Figu e 5.2.1 a) Molecula s uc u e o 2. The hyd ogen bonds a e d awn as o ange dashed lines. The asymme ic uni consis s o only hal o he molecule. The o he hal gene a ed h ough he cen e o symme y is d awn in ligh colou s. Symme y code: i: 1 – x, 1 – y, 1 – z. The he mal ellipsoids a e d awn a he 50 % p obabili y le el. b) The c ys al s uc u e o 2 held by hyd ogen bonding sys em (o ange dashed lines); he bc plane is depic ed. Table 5.2.1 Po en ial hyd ogen bonds in 2. D-H···A D-H [Å] H···A [Å] D···A [Å] D-H···A [°] N1-H1A···Cl1i 0.89 2.28 3.169 (4) 174 N1-H1B···Cl1ii 0.89 2.25 3.142 (4) 177 N1-H1C···Cl1iii 0.89 2.32 3.197 (4) 167 Symme y codes: i: 1 – x, – 1/2 + y, 1/2 – z; ii: x, 1/2 – y, 1/2 + z; iii: – 1 + x, y, z. The second syn he ic expe imen wi h in si u app oach we will men ion in his wo k is he eac ion o cobal (II) ca bona e, dysp osium(III) chlo ide and H2(o- an-en) ligand whe e as in he p e ious case, e hanol was used as sol en . The eac ion sys em was s i ed and hea ed o 80 °C and a e 15 minu es, he solid p oduc p ecipi a ed. The e-c ys alliza ion expe imen s we e no success ul, only he expe imen o he di usion o he e hanol solu ion in o isop opanol yielded he c ys alline o m o he side p oduc 1,5-dica boxy-2-hyd oxy-3-me hoxybenzene (3). This compound may be he esul o se e al po en ial p ocesses, including he decomposi ion o he Schi base ligand H2(o- an-en) yielding back o- anillin, oxida ion o he aldehyde g oup o o- anillin and inally, ca boxyla ion o he p e ious in e media e. This hypo hesis is based on he 51 assump ion ha he excess o CO32- coming om cobal (II) ca bona e is he o igin o he acidic medium and also caused he inal ca boxyla ion. The 1,5-dica boxy-2-hyd oxy-3-me hoxybenzene (3) c ys allizes in he o ho hombic space g oup Pbca. I s molecula s uc u e consis s o one molecule o 1,5- dica boxy-2-hyd oxy-3-me hoxybenzene wi h one H a om o he ca boxylic g oup in he i h posi ion o he a oma ic ing posi ionally diso de ed be ween he wo O a oms o he same ca boxy g oup (Fig. 5.2.2a). The delocaliza ion can be clea ly seen in he di e ence map in Fig. 5.2.3. The eal posi ion o he H34 a om indica ed by he diag am is loca ed be ween O3 and O4 o he neighbou ing molecule. I should be no ed ha his compound in he o m o he dihyd a e was al eady epo ed in he li e a u e [Vladimi o a e al., 2016]. a) b) Figu e 5.2.2 a) The molecula s uc u e o 3. Bo h H-a oms, H34A and H34B a e p esen (wi h occupancy ac o being 0.5). The he mal ellipsoids a e d awn a he 50 % p obabili y le el. b) The c ys al s uc u e o 3 held by hyd ogen bonding sys em (o ange dashed lines); he ac plane is depic ed. 52 Figu e 5.2.3 The di e ence map diag am showing he elec on densi y a ound he a oms H34B-O3-C8-O4-H34A o he diso de ed ca boxylic g oup. Table 5.2.2 Po en ial hyd ogen bonds in 3. D-H···A D-H [Å] H···A [Å] D···A [Å] D-H···A [°] O1-H1···O2 0.82 2.09 2.571 (3) 117 O1-H1···O6i 0.82 2.19 2.973 (4) 160 O3-H34B···O4ii 0.82 2.46 3.150 (4) 143 O4-H34A···O3iii 0.82 2.44 3.150 (4) 145 C3-H3···O4ii 0.93 2.49 3.409 (4) 170 C5-H5···O3iii 0.93 2.53 3.453 (4) 170 Symme y codes: i: – 1/2 + x, 1/2 – y, 1 – z; ii: – 1/2 + x, y, 3/2 – z; 1/2 + x, y, 3/2 – z. In conclusion, one canno say ha his ype o eac ion was no p oduc i e bu besides ou desi ed p oduc we isola ed also se e al side p oduc s esul ing om he decomposi ion o he ligand. The p esence o he side p oduc con amina es he inal p oduc and lowe s i s yield. A e his ini ial in es iga ion, he syn heses o he e odinuclea {T -Ln} complexes we e conduc ed using he s epwise app oach schema ically depic ed in he Scheme 5.2.1. The sel -assembly p epa a ion me hod was designed conside ing gene al eac ion pa hways summa ized in [Cos es e al., 1997]; Schi eac ion condi ions desc ibed in [Ghose, 1984] we e aken in accoun and 59 The iden i y o he p epa ed mic oc ys alline p oduc was de e mined by he Le Bail e inemen o he pa e n calcula ed using bo h se s o s uc u al da a o 4 compa ed wi h i s measu ed powde di ac ion pa e n using he p og am Jana2006 [Le Bail e al., 1988; Le Bail, 2005; Pe říček e al., 2014]. We no e ha he expe imen al powde di ac ion da a was collec ed a oom empe a u e. Using he oom- empe a u e CIF ile, he ollowing esul s we e ob ained (Fig. 5.2.1.5). In he Pseudo-Voig unc ion, Gaussian pa ame e s U (basic b oadening by sli s), V (wa e leng h dispe sion) and W (in luence o monoch oma o ) and Lo en zian pa ame e X (pa icle b oadening) we e e ined. Peak asymme y was co ec ed using he Bé a -Baldinozzi model wi h 4 pa ame e s; he i s h ee we e e ined and he ou h was ixed. Backg ound was co ec ed using Legend e polynomials (10 e ms) and by e ining he shi pa ame e . The e ined cell pa ame e s o o ho hombic space g oup Pbcn a e ( he alues om he CIF a e gi en in b acke s) a = 19.624 (3) [19.6427 (8)] Å, b = 11.873 (2) [11.8972 (5)] Å, c = 15.224 (3) [15.2443 (8)] Å. The esul ing R- alues a e R(p) = 0.0172, R(wp) = 0.0258 and goodness o i = 8.34. Using he low- empe a u e CIF ile, he e ined cell pa ame e s o o ho hombic space g oup Pbcn a e ( he alues om he CIF a e gi en in b acke s) a = 19.6059 (15) [19.6607 (6)] Å, b = 11.8568 (9) [11.8032 (4)] Å, c = 15.2096 (12) [15.0266 (4)] Å. The esul ing R- alues a e R(p) = 0.0230, R(wp) = 0.0359 and goodness o i = 11.58. The e inemen was done using he Pseudo-Voig unc ion, Gaussian pa ame e s V, W and P (Sche e coe icien ) and Lo en zian pa ame e s X and Y (s ain b oadening) we e e ined. The peak asymme y due o axial di e gence was co ec ed by Jana2006, oo. As in he p e ious e inemen , backg ound was co ec ed using Legend e polynomials (10 e ms) and by e ining he shi pa ame e . 60 a) b) Figu e 5.2.1.5 Resul s o Le Bail e inemen o he powde di ac ion pa e n o 4, wi h he s a ing uni -cell pa ame e s aken om he a) oom- empe a u e, b) low- empe a u e da a se . Obse ed da a a e black, calcula ed da a a e d awn as ed. 61 [Ni(o- an-en)]·H2O·E OH (5) The molecula s uc u e o 5 con ains he same complex molecule [Ni(o- an-en)] like he p e ious compound. The nickel(II) cen al a om lies in he squa e plana inne coo dina ion si e o he Schi base ligand (o- an-en)2- wi h he {O2N2} dono se . The Ni–O and Ni–N bond dis ances a e in line wi h hose o he p e iously commen ed c ys al s uc u es (Tab. 5.2.1.1). The ou e ca i y o he ligand is occupied by a ela i ely s ongly ancho ed wa e sol a e molecule. The wa e molecule is bonded by wo bi u ca ed-dono hyd ogen bonds o he O–H···O ype o all ou oxygen a oms o he Schi base ligand. In addi ion, he asymme ic uni o 5 con ains an e hanol sol a e molecule, hyd ogen bonded o he wa e sol a e men ioned abo e (Fig. 5.2.1.6a). The O6 oxygen a om o he e hanol sol a e o ms wo hyd ogen bonds in wo di e en di ec ions, which is p obably he cause o i s posi ional diso de ep esen ed by O6A and O6B a omic si es. Addi ionally o he abo e men ioned hyd ogen bonds, he c ys al s uc u e o 5 consis s o ich sys em o weake in e molecula o ces. Howe e , e hanol sol a e molecules a e loca ed in ce ain channels along he a axis and bonded weakly enough o mo e ac oss he c ys al s uc u e. This is he p obable cause o he low s abili y o c ys als o 5 a oom empe a u e ou o i s mo he liquo . Hyd ogen bonds o he wa e sol a e molecule men ioned abo e oge he wi h he weake C8–H8···O5i (i = – x, 1 – y, 1 – z) hyd ogen bond and po en ial Cg1···Ni1iii (iii = 1 – x, 1 – y, 1 – z) ing-me al in e ac ion o m sup amolecula dime ic uni s o {[Ni(o- an-en)]·H2O}2. Ring···me al dis ance in he ing-me al in e ac ion men ioned abo e is 3.545 Å, he pe pendicula dis ance is 3.333 Å and he β angle equals 19.92°. Dime ic uni s a e hen connec ed by hyd ogen bonding sys em wi h e hanol sol a e molecules in he b di ec ion and Ni1···Ni1iii in e ac ions (me al-me al dis ance is 3.3379 (3) Å) in he a di ec ion o ming sup amolecula laye s pa allel o he ab plane (Fig. 5.2.1.6b); Tab. 5.2.1.4). The obse ed sho NiNi dis ances may co espond o me al-me al in e ac ions [Thomas & Unde hill, 1972; Siegle & Lu z, 2009]. 62 a) b) Figu e 5.2.1.6 a) The asymme ic uni o 5 along wi h he a om numbe ing scheme. The he mal ellipsoids a e d awn a he 50 % p obabili y le el. The second diso de ed posi ion o O6 (O6B) is depic ed in a ligh colou o cla i y. b) The packing diag am o 5. Po en ial hyd ogen bonds, ing-me al and me al-me al in e ac ions a e deno ed as o ange, blue and g een dashed lines, espec i ely. Fo cla i y, hyd ogen a oms no in ol ed in hyd ogen bonds a e omi ed and ca bon a oms a e d awn in „s icks“ model. 63 Table 5.2.1.4 Po en ial hyd ogen bonds in 5. D–H···A D–H [Å] H···A [Å] D···A [Å] D–H···A [°] O5–H5A···O1 0.79 (3) 2.23 (3) 2.9021 (18) 143 (2) O5–H5A···O2 0.79 (3) 2.23 (3) 2.9247 (16) 146 (2) O5–H5B···O3 0.76 (3) 2.40 (2) 2.9726 (16) 134 (2) O5–H5B···O4 0.76 (3) 2.14 (3) 2.8483 (18) 155 (2) O6A–H6···O5 0.79 (3) 1.94 (3) 2.699 (6) 163 (3) O6B–H6···O5 0.87 (4) 1.94 (3) 2.724 (13) 151 (4) C8–H8···O5i 0.952 (19) 2.549 (18) 3.226 (2) 128.2 (14) C11–H11···O6Aii 0.938 (18) 2.63 (2) 3.496 (8) 153.8 (14) Symme y codes: i: – x, 1 – y, 1 – z; ii: x, 1 + y, z. [Ni(o- an-en)]·H2O·iP OH (6) The hi d compound o he Ni-(o- an-en) se ies, compound 6 has a simila molecula s uc u e o he wo p e ious compounds 4 and 5. I s asymme ic uni consis s o he same [Ni(o- an-en)] complex molecule and wa e sol a e molecule loca ed in he ou e coo dina ion si e o he Schi base ligand (o- an-en)2- as dono in wo bi u ca ed hyd ogen bonds. Addi ionally, i possesses one isop opanol sol a e molecule which is hyd ogen-bonded o he abo e men ioned wa e sol a e (Fig. 5.2.1.7a). Simila ly o 5, he c ys al s uc u e o 6 con ains dime ic uni s o complex molecules [Ni(o- an-en)]2 which a e held by me al-me al in e ac ion be ween Ni(II) cen al a oms. The me al-me al dis ance wi hin he sup amolecula dime is 3.3714 (6) Å. A iew o he dime om abo e shows ha he π sys ems o he a oma ic ings do no o e lap (Fig. 5.2.1.7b). Addi ionally, he sup amolecula dime s a e connec ed by weak in e molecula o ces be ween a oma ic ings o med by C2 – C7 a oms and Ni(II) cen al a oms o he neighbou ing complex molecules, o ming sup amolecula chains along he b axis (Fig. 5.2.1.7c), d). The 3D c ys al packing is suppo ed only by weak in e molecula o ces. 64 a) b) c) d) Figu e 5.2.1.7 a) Molecula s uc u e o 6 along wi h he a om numbe ing scheme. Hyd ogen bonds a e depic ed as o ange dashed lines. b) View om abo e a sup amolecula dime o med by me al-me al in e ac ion. The lowe molecule is depic ed in ligh colou s o cla i y. c), d) The packing diag ams o 6 – he bc and ac plane iew, espec i ely. 65 Table 5.2.1.5 Po en ial hyd ogen bonds in 6. D–H···A D–H [Å] H···A [Å] D···A [Å] D–H···A [°] O5–H5A···O1 0.78 (6) 2.11 (6) 2.778 (4) 144 (6) O5–H5A···O2 0.78 (6) 2.49 (6) 3.057 (3) 131 (5) O5–H5B···O3 0.77 (4) 2.45 (4) 3.060 (4) 138 (4) O5–H5B···O4 0.77 (4) 2.09 (5) 2.784 (4) 150 (4) O6–H6···O5 0.67 (4) 2.16 (4) 2.819 (4) 169 (5) 66 5.2.2 {Co(II)/Co(III) – (o- an-en)} complexes In an a emp o p epa e he Co(II)-Ln dinuclea complexes, we ied se e al syn he ic ou es leading o isola ion o p ecu so s con aining he [CoII(o- an-en)] uni . We no e ha he li e a u e epo s he [CoII(o- an-en)(H2O)] complex which was p epa ed by in si u sol o he mal syn hesis s a ing om 2-hyd oxy-3-me hoxy- benzaldehyde, e hane-1,2-diamine and cobal (II) ni a e [Jiang e al., 2007]. Va ying he syn he ic condi ions we ha e isola ed 3 di e en p oduc s, including he abo e men ioned one. The p e iously epo ed complex [CoII(o- an-en)(H2O)] (7) was isola ed in mic oc ys alline o m by he di ec eac ion o cobal (II) hyd oxide wi h he Schi base H2(o- an-en) using mild condi ions unde an ine a gon a mosphe e. The o ange mic oc ys alline sample, isola ed om he mo he liquo is s able in ai , esis an o a con ingen oxida ion. An a emp o ec ys allize he mic oc ys alline p oduc 7 om ace oni ile a oom empe a u e in he p esence o ai led o oxida ion o Co(II) o Co(III) and o ma ion o he monoclinic o m o [CoIII2(o- an-en)3]4CH3CN (8). Di ec eac ion o he Schi base wi h Co(OH)2 in he p esence o ai led o a black mic oc ys alline c ude p oduc ; he colou change clea ly indica ed oxida ion o Co(II) o Co(III). When he esul ing c ude p oduc was ec ys allized om ho ace oni ile, c ys als o he iclinic o m o [CoIII2(o- an-en)3]4CH3CN (9) we e sepa a ed. We no e ha bo h o ms o he newly p epa ed complex [CoIII2(o- an-en)3]4CH3CN (8, 9) a e uns able ou side o he mo he liquo . Following ou s a egy o he s epwise eac ion, he complex [CoII(o- an-en)(H2O)] (7) p o ed o be he bes candida e o a [T (o- an-en)] p ecu so o he las s ep. Using he gadolinium chlo ide as an ini ial sou ce o he lan hanide, we ca ied ou he syn heses unde mild condi ions in e hanol and ace oni ile, espec i ely. In bo h cases, he lan hanide a om did no en e he coo dina ion si e o he Schi base ligand. In addi ion, we isola ed and iden i ied he oxidised p oduc s o he eac ions. Complexes [CoIII(o- an-en)(H2O)Cl] (10) and [CoIII(o- an-en)(H2O)Cl]·2CH3CN (11) we e isola ed in c ys alline o m, a ailable o X- ay di ac ion analysis. [CoII(o- an-en)(H2O)] (7) The iden i y o he p oduc 7 p epa ed by us and ha epo ed by Jiang e al. was co obo a ed by compa ison o he measu ed powde di ac ion pa e n wi h he pa e n 67 calcula ed using he s uc u al da a epo ed by Jiang e al. [2007]. Fo a de ailed compa ison, he Le Bail e inemen was applied using he p og am Jana2006 (Fig. 5.2.2.1) [Le Bail e al., 1988; Le Bail, 2005; Pe říček e al., 2014]. In his case, he bes app op ia e leas -squa es- i ed peak p o ile op ion was he Pseudo-Voig unc ion, con olu ing he Gaussian and Lo en zian unc ions. Gaussian pa ame e s we e no used excep he W pa ame e (in luence o monoch oma o ). Pa icle and s ain b oadening was i ed by using bo h, X and Y pa ame e s o he Lo en zian pa o he i ing peak- shape unc ion. The peak asymme y due o axial di e gence was co ec ed by Jana2006, oo. The e ined cell pa ame e s o o ho hombic space g oup Pnma a e ( he alues epo ed by Jiang e al., 2007 a e gi en in b acke s) a = 8.9941(18) [8.9827 (6)] Å, b = 24.970(4) [24.8632 (16)] Å, c = 7.7011(9) [7.5784 (5)] Å. The ob ained R- alues a e R(p) = 0.0541, R(wp) = 0.0754 and goodness o i = 1.91. Figu e 5.2.2.1 Resul s o Le Bail e inemen o he powde di ac ion pa e n o 7, wi h he s a ing uni -cell pa ame e s aken om he known c ys al s uc u e o [Co(o- an-en)(H2O)] [Jiang e al., 2007]. Obse ed da a a e black, calcula ed da a a e d awn as ed. The molecula s uc u e o 7 is buil up o complex [CoII(o- an-en)(H2O)] molecules. The cen al Co(II) a om is pen acoo dina ed, wi h he N2O2 dono a oms om he Schi base ligand occupying he basal plane o he squa e py amid while he apical posi ion is occupied by he aqua ligand (Fig. 5.2.2.2a). We no e ha he obse ed 68 posi ional diso de o he ca bon a oms om he e hylenediamine pa o he Schi base ligand is imposed by he p esence o a mi o plane (space g oup is Pnma) cu ing he complex in wo symme ic hal es. The sup amolecula s uc u e is o med by zig-zag hyd ogen bonded (O–H···O ype) chains (Fig. 5.2.2.2b). P opaga ion o he c ys al s uc u e in all h ee dimensions is ealized by weak C–H···C close con ac s and π-π s acking in e ac ions. a) b) Figu e 5.2.2.2 a) The molecula s uc u e o he complex [CoII (o- an-en)(H2O)] (7) published by Jiang e al. The second posi ion o he posi ional diso de is d awn in ligh colou ; b) he zig-zag sup amolecula chains in he c ys al s uc u e o 7. Hyd ogen bonds a e deno ed as o ange dashed lines. Fo cla i y, hyd ogen a oms no in ol ed in hyd ogen bonds a e omi ed and ca bon a oms a e d awn in „s icks“ model [Jiang e al., 2007]. [CoIII2(o- an-en)3]4CH3CN ( o m I = 8, o m II = 9) Bo h o ms o [CoIII2(o- an-en)3]4CH3CN ( o m I = 8, o m II = 9), isola ed unde ae obic condi ions we e c ys allog aphically s udied as polymo phs. Along wi h he de ailed cha ac e iza ion o hei c ys al and molecula s uc u es, he wo 75 oxygen a om O1 (ci cled in Fig. 5.2.2.6a). The oxygen a om o his o ien a ion o he me hoxy g oup is mo e exposed on he su ace o he complex molecule which is also e lec ed on he co esponding FIM. a) b) Figu e 5.2.2.6 a) FIM o complex molecules o 8. H-bond dono egions a e ep esen ed in blue; accep o egions a e ed. Do s, wi e ame and solid egions ep esen equencies o 2, 4 and 6 imes hose expec ed o a andom dis ibu ion o con ac s. b) En i onmen s o wo symme ically independen dono egions in he FIM o compound 8. Only he 4- and 6- imes le els a e shown. 76 In compound 8, he accep o egion nea he dono C11-H11 imine g oup, pic u ed in he FIM as a ed egion, is no ully occupied, unless he nea by elec on densi y o he π-sys em o he a oma ic ing C2iii - C7iii can be conside ed as a po en ial H-accep o (le ci cle in Fig. 5.2.2.6b). Howe e , his a oma ic ing is in ol ed in a weak C-H···π in e ac ion wi h Ca 21-H21 o he adjacen b idging ligand (Tab. 5.2.2.2). The accep o egion o he C8-H8 imine g oup is no occupied by any accep o g oup ( igh ci cle in Fig. 5.2.2.6b). Jus like o compound 8 (Fo m I), he FIM o he complex molecule in 9 (Fo m II) shows ou egions wi h a s ong p esence o H-bond accep o s in known s uc u es ( ed egions in Fig. 5.2.2.7a), wo pe asymme ic uni ), e lec ing he dono capabili ies o he CH imine g oups C8-H8 and C11-H11 and hei symme y ela i es. The only possible accep o si es (me hoxy and oxy g oups) a e o ien ed owa d he in e io o he complex molecule, mos ly o ming in amolecula in e ac ions, so he FIM does no show any po en ial dono egion. In compound 9, he dono C8-H8 imine g oup is in ol ed in a a he weak in e molecula close con ac C8-H8···O5i (le ci cled in e ac ion in Fig. 5.2.2.7b), beyond he de aul limi s o PLATON, and simila ly, he dono si e a he C11-H11 imine g oup is in ol ed in a weak C-H···π in e ac ion ( igh ci cled in e ac ion in Fig. 5.2.2.7b), also beyond he PLATON con en ional limi s. I is sugges ed ha hese in e ac ions, weak hough hey be, ac as di ec o s o he packing o complex molecules in he s uc u e o 9. 77 a) b) Figu e 5.2.2.7 a) FIM o complex molecules o 9. H-bond dono egions a e ep esen ed in blue; accep o egions a e ed. Do s, wi e ame and solid egions ep esen equencies o 2, 4 and 6 imes hose expec ed o a andom dis ibu ion o con ac s. b) En i onmen s o wo symme ically independen dono egions in he FIM o compound 9. Only he 4- and 6- imes le els a e shown. In gene al, in 8 and 9, he s onges egions o in e molecula in e ac ions in he FIMs a e occupied by symme y ela ed molecules media ed by weak C-H···O ype hyd ogen bonds and C-H···π in e ac ions o no occupied a all. None o he in e ac ions men ioned abo e lies exac ly in he in e ac ion egion ( he accep o is oo a away). MeCN molecules do no en e he dono o accep o egions o he complex molecules in ei he o hese wo polymo phs. F om he FIM analysis we can conclude ha he complex molecule [CoIII2(o- an-en)3] ( o bo h o ms, I and II) does no possess a s ong capaci y o sel - ecogni ion wi h signi ican in e ac ions. E en hough he molecules eco d ou egions 78 wi h signi ican capaci y o H-bond dona ion hey a e no ma ched by any segmen s wi h he co esponding capaci y o accep hyd ogen bonds. In e molecula in e ac ions in 8 and 9 a e a he ene ge ically poo and he e o e, he polymo phism o [CoIII2(o- an-en)3]·4MeCN is no a esul o a su ei o molecula a angemen s leading o highly s abilizing in e ac ions. Acco ding o he abo e men ioned conside a ions and hei low s abili y ou side o hei mo he liquo a he empe a u e a which hey a e o med, i is no su p ising ha he e would be mo e han one way o achie e a lesse le el o s abili y. The Hi sh eld su ace analysis and inge p in plo s o he wo polymo phs we e done in an a emp o ha e a de ailed g aphical iew o he wo polymo phic o ms. Unlike he FIM analysis, he Hi sh eld su ace shows only he ac ual in e molecula in e ac ions o he [CoIII2(o- an-en)3] complex molecule. The Hi sh eld su aces o bo h, 8 and 9 a e isualized in Fig.5.2.2.8a)-d). In bo h cases he s uc u es su e mino diso de . Because he simul aneous p esence o wo diso de ed g oups o he same diso de assembly will gene a e he appea ance o a i icial and impossibly sho con ac s in he Hi sh eld su aces and inge p in plo s we will p o ide he analysis o each diso de ed pa sepa a ely. The dis ibu ions o in e molecula in e sec ions o Van de Waals´s su aces ( ed a eas) in he wo se s o plo s gi e a clea quali a i e indica ion ha he in e molecula spaces in he wo s uc u es a e o ganized in di e en ashions. We no e ha in 8, he C1 me hoxy g oup is posi ionally diso de ed o e wo posi ions wi h hal occupancies. The eason o his diso de is ob ious om Fig. 5.2.2.8a) displaying he Hi sh eld su ace; he C1 me hyl g oup in posi ion A (a om C1A) o ms a close con ac o i s symme y (-1) gene a ed congene (C1AC1A is 2.364(11) Å, is –x, 1 - y, 1 - z) which mani es s i sel as a s ong ed spo . The si ua ion o he second diso de ed posi ion, labelled B is shown on he Fig. 5.2.2.8b); he abo e men ioned ed spo is missing; on he o he hand, he second diso de ed posi ion o his me hoxy g oup (O1-C1B) is close o an MeCN sol a e molecule which mani es s i sel by a weak hyd ogen bonding in e ac ion o he C-HN ype wi h N4 o he MeCN molecule (Tab. 5.2.2.2). We no e ha in his diso de ed posi ion B an addi ional in amolecula hyd ogen bonding in e ac ion o he C-HO ype (C1B- H1BB···O2) is o med, oo. The abo e men ioned close con ac s can be in e p e ed also by Finge p in plo s [Spackman & McKinnon, 2002] gene a ed by Hi sh eld su ace o 79 dinuclea complex molecule o 7 (diso de A and B) (Fig. 5.2.2.9). The closes con ac obse ed in diso de A associa ed wi h C1A me hoxy g oup co esponds o sho HH, CC and CH con ac s wi h sho di+de sums up o 2.4 Å, displaying as wo lobes a he lowe le pa o he diag am. This ea u e is na u ally missing in he Finge p in plo o diso de ed posi ion B. On he o he hand, in he case o he second diso de ed me hyl posi ion o 7 labelled B he wo abo e-men ioned weak hyd ogen bonds o C-HN and C-HO ypes o med which leads o a ce ain inc ease o he OH/HO and NH/NH ype close con ac s displayed on co esponding Finge p in plo s (11.5 s. 12.6 % and 9.3 s. 9.5 %, espec i ely). In addi ion, Fig. 5.2.2.8a),b) shows ha he MeCN sol a e molecules a e loca ed in he hollows on he su ace o he complex molecules and hus con ibu e o be e illing o he in e molecula space (packing) in he uni cell which in u n acco ding o Ki aigo odskii con ibu es o he s abiliza ion o he s uc u e [Ki aigo odskii, 1965]. We no e ha calcula ions using PLATON indica ed a lack o any accessible oids in he c ys al s uc u e o 8. The calcula ed Hi sh eld su ace o he dinuclea complex molecule o 9 is shown in Fig. 5.2.2.8c) and d). In 9 he MeCN molecule in ol ing N5 (as well as C31) is posi ionally diso de ed wi h si e occupa ion ac o s close o hal (0.43 and 0.57 o N5A and N5B a oms, espec i ely); he le igu e shows he si ua ion wi h he MeCN molecule in A posi ion (a oms N5A and C31A) and he igh igu e displays he same MeCN molecule in diso de ed posi ions B (a oms N5B and C31B). As he diso de pe ains only o he sol a e molecule and, in addi ion, he wo diso de ed posi ions a e close o each o he (N5AN5B dis ance is 1.29 (3) Å), he Hi sh eld su aces o he complex molecules o bo h si ua ions a e no a ec ed. The only di e ence is ha in he diso de ed posi ion N5A a weak hyd ogen bonding in e ac ion C18-H18AN5A is o med while a sligh ly s onge in e ac ion C5-H5N5B is o med in diso de ed posi ion N5B (see ed dashed lines on Fig. 5.2.2.8c),d). We no e ha he second in e ac ion (N5B) is in ol ed in he Tab. 5.2.2.3 while he i s one in ol ing N5A is no as he H18AN5A con ac (2.66 Å) is beyond PLATON´s limi o hyd ogen bonding in e ac ion. In line wi h his obse a ion he posi ion N5B is sligh ly mo e popula ed han he i s one wi h N5A. The calcula ed inge p in plo s o 9 (Fig. 5.2.2.9) also e lec he di e ences o he wo diso de ed posi ions o he MeCN molecules, i.e. conce n mainly he NH con ac s as hese a e a ec ed by he p esen 80 diso de in he s uc u e. These con ac s a e sho e in he inge p in plo s o N5B wi h espec o N5A. E en hough he Hi sh eld su ace analysis g aphically in e p e s he di e ences be ween he con o ma ions and di e en in e molecula con ac s his does no gi e us a clea indica ion o he o igins o he polymo phism. To explo e ha ques ion, he Full In e ac ion Maps analysis comes ou as a be e me hod. a) b) c) d) Figu e 5.2.2.8 Hi sh eld su aces o he dinuclea complex molecules o 8 (a,b) and 9 (c,d) plo ed o e dno m (no malised con ac dis ance) om -0.4000 o 1.5000 a.u. MeCN sol a e molecules a e displayed in g een. Close con ac s (O∙∙∙H ≤ 2.60 Å, N∙∙∙H ≤ 2.63 Å) a e shown as ed dashed lines. The neighbou ing molecules a e d awn using wi e models in di e en colou s in o de o ha e a be e iew o he con ac s. 81 8(A) O∙∙∙H/H∙∙∙O 11.5 % N∙∙∙H/H∙∙∙N 9.3 % C∙∙∙H/H∙∙∙C 26.3 % 8(B) O∙∙∙H/H∙∙∙O 12.6 % N∙∙∙H/H∙∙∙N 9.5 % C∙∙∙H/H∙∙∙C 26.3 % 9(A) O∙∙∙H/H∙∙∙O 11.8 % N∙∙∙H/H∙∙∙N 9.7 % C∙∙∙H/H∙∙∙C 25.8 % 9(B) O∙∙∙H/H∙∙∙O 12.2 % N∙∙∙H/H∙∙∙N 8.4 % C∙∙∙H/H∙∙∙C 25.8 % Figu e 5.2.2.9 Finge p in plo s o dinuclea complex molecules o 8 and 9, wo di e en diso de s o bo h s uc u es. 82 [CoIII(o- an-en)(H2O)Cl] (10) and [CoIII(o- an-en)(H2O)Cl]·2MeCN (11) The molecula s uc u es o bo h, [CoIII(o- an-en)(H2O)Cl] (10) and [CoIII(o- an-en)(H2O)Cl]·2MeCN (11) con ain o he [CoIII(o- an-en)(H2O)Cl] complex molecules. Compound 11 addi ionally con ains wo c ys allog aphically independen MeCN sol a e molecules. The Co(III) cen al a om in he complex molecule is coo dina ed by he chela ing Schi base ligand (o- an-en)2- wi h he {N2O2} dono se in he equa o ial plane and he hexacoo dina ion o he cen al a om is comple ed by aqua and chlo ido ligands in axial posi ions (Figs. 5.2.2.10a) and 5.2.2.11a). The Co-O, Co-N and Co-Cl bond dis ances ound in bo h 10 and 11 a e in he ange o he co esponding alues ound in [CoIII(o- an-en)(H2O)Cl]·DMF [Wei e al., 2012] (Tab. 5.2.2.4). We no e ha he alues ound in he epo ed c ys al s uc u e o [CoIII(o- an-en)(H2O)Cl]·H2O [Xing, 2009] de ia e om expec ed bond leng hs o a Co(III) a om in he co esponding coo dina ion. Table 5.2.2.4 Selec ed bond leng hs [Å] o 10 and 11 compa ed wi h co esponding alues ound in [CoIII(o- an-en)(H2O)Cl]·DMF (a) [Wei e al., 2012] and [CoIII(o- an- en)(H2O)Cl]·H2O (b) [Xing, 2009]. 10 11 a b Co1-O2 1.900 (2) 1.898 (3) 1.885 (2) 1.863 (3) Co1-O3 1.907 (2) 1.901 (2) 1.887 (3) 1.868 (3) Co1-N1 1.885 (3) 1.894 (3) 1.884 (3) 1.957 (4) Co1-N2 1.878 (3) 1.887 (3) 1.883 (3) 1.932 (4) Co1-O5 1.967 (2) 1.962 (3) 1.982 (2) 2.324 (3) Co1-Cl1 2.2197 (10) 2.2279 (11) 2.2193 (11) 2.5513 (17) The [CoIII(o- an-en)(H2O)Cl] (10) complex c ys allizes in he o ho hombic space g oup Pbca. I s c ys al s uc u e is o med by sup amolecula [CoIII(o- an-en)(H2O)Cl]2 dime ic uni s held by ou hyd ogen bonds o he O-H···O ype be ween he aqua ligand o he one complex molecule (x, y, z) and he oxygen a oms o he (o- an-en)2- ligand o a second congene (1 – x, 1 – y, 1 – z) gene a ed h ough he cen e o symme y loca ed in he middle (Fig. 5.2.2.10b). Due o hese hyd ogen bonds, he aqua ligand occupies he ou e coo dina ion si e o he Schi base ligand. The in e molecula in e ac ions in he dime men ioned abo e a e suppo ed by he π···π s acking in e ac ions be ween he a oma ic ings o he Schi base ligand. The 83 co esponding hyd ogen bonds and π-π s acking in e ac ions p esen in he dime a e lis ed in Tab. 5.2.2.5. An addi ional C11-H11···Cl1ii weak hyd ogen bond links he dime s in o sup amolecula laye s in he ac plane in he c ys al s uc u e o 10 (Fig. 5.2.2.10c). The [CoIII(o- an-en)(H2O)Cl]·2MeCN (11) complex c ys allizes in he monoclinic space g oup P21/n. I s c ys al s uc u e con ains he same ype o sup amolecula dime ic uni s as hose in he s uc u e o 10 (Fig. 5.2.2.11b). The co esponding hyd ogen bonds p esen in he dime a e lis ed in Tab. 5.2.2.6. In addi ion, bo h C8-H8 and C11-H11 imine g oups o he Schi base ligand a e in ol ed in hyd ogen bonding in e ac ions o he C-H···N ype wi h he wo N3 and N4 a oms o MeCN sol a e molecules, espec i ely (Tab. 5.2.2.6). The 3D sup amolecula s uc u e is held only by weak in e molecula close con ac s o he C-H···X ype whe e X = O, N o Cl. 84 a) b) c) Figu e 5.2.2.10 a) The asymme ic uni o [CoIII(o- an-en)(H2O)Cl] (10) wi h he a om numbe ing scheme. The he mal ellipsoids o non-hyd ogen a oms a e d awn a he 50 % p obabili y le el. b) The sup amolecula dime in 10. The second congene o he dime is d awn in ligh colou s and H-a oms no in ol ed in hyd ogen bonds a e no shown o cla i y. Hyd ogen bonds and π···π s acking in e ac ions a e d awn as o ange and blue dashed lines, espec i ely. c) Packing diag am o 10. The ac plane is shown. Ca bon a oms a e d awn in s ick model and H-a oms no in ol ed in hyd ogen bonding (o ange dashed lines) a e no shown o cla i y. 91 Table 5.3.1 Selec ed bond leng hs in Ni-Gd bime allic complexes 12, [NiLGd(NO3)3] (a) [Wen e al., 2015] and [Ni(MeOH)2LGd(NO3)3]∙2MeOH (b) [Jana e al., 2010]. 12 a b Ni1–O2 1.851 (9) 1.851 (9) 2.027 (2) Ni1–O3 1.865 (8) 1.856 (9) 2.037 (2) Ni1–N1 1.870 (10) 1.840 (12) 2.034 (2) Ni1–N2 1.826 (11) 1.852 (10) 2.018 (3) Gd1–O1 2.528 (8) 2.525 (8) 2.540 (2) Gd1–O2 2.368 (8) 2.365 (9) 2.323 (2) Gd1–O3 2.442 (8) 2.398 (9) 2.319 (2) Gd1–O4 2.546 (9) 2.530 (8) 2.552 (2) Gd1–O5 2.497 (8) 2.477 (11) 2.638 (4) Gd1–O6 2.448 (9) 2.483 (9) 2.506 (3) Gd1–O8 2.559 (9) 2.500 (10) 2.582 (3) Gd1–O9 2.477 (8) 2.509 (10) 2.482 (3) Gd1–O11 2.464 (10) 2.509 (9) 2.488 (3) Gd1–O12 2.476 (7) 2.520 (9) 2.589 (3) Table 5.3.2 Po en ial hyd ogen bonds and π-π s acking in e ac ions in 12. D–H···A D–H [Å] H···A [Å] D···A [Å] D–H···A [°] C4–H4···O5i 0.95 2.43 3.277 (15) 148 C11–H11···N6ii 0.82 (14) 2.60 (14) 3.37 (2) 158 (13) C13–H13···O5ii 0.95 2.58 3.433 (16) 150 C15–H15···O11iii 0.95 2.56 3.372 (17) 143 π···π Cg···Cg [Å] α [°] β [°] γ [°] Slippage [Å] Cg1···Cg2i 3.720 (2) 9.2 (2) 18.0 21.3 1.152 Symme y codes: i: x, y, 1 + z; ii: 3/2 – x, –1/2 + y, –1/2 + z; iii: x, y, –1 + z. Cg1 is he cen e o g a i y o he a oma ic ing o med by C2 – C7 a oms; Cg2 is he cen e o g a i y o he a oma ic ing o med by C12 – C17 a oms. 92 a) b) Figu e 5.3.1 a) The molecula s uc u e o 12 along wi h i s a om numbe ing scheme. The he mal ellipsoids o non-hyd ogen a oms a e d awn a he 50 % p obabili y le el. b) C ys al s uc u e o 12. The bc plane is pic u ed. Hyd ogen bonds and π···π s acking in e ac ions a e d awn as o ange and blue dashed lines, espec i ely. 93 [Ni(o- an-en)LnCl3(H2O)] (Ln = Ce in 13, Gd in 14, Dy in 15) Compounds 13 – 15 a e isomo phous, so we will limi ou desc ip ion and discussion o complex 13 wi h he co esponding geome ic pa ame e s o 14 and 15 gi en in pa en heses. The molecula s uc u e o 13 consis s o neu al he e odinuclea complex molecules o [Ni(o- an-en)Ce(H2O)Cl3] (Fig. 5.3.2a). The Ni(II) a om is coo dina ed in squa e-plana o m by he {N2O2} dono se o he po en ially di opic ligand (o- an-en)2-. The Ce(III) cen al a om is oc acoo dina ed by ou oxygen a oms om he (o- an-en)2- ligand, one aqua and h ee chlo ido ligands, yielding an {LnCl3O5} ch omopho e. The obse ed Ni–N and Ni–O as well as he Ce–O bond dis ances a e simila o hose epo ed in he analogous complexes [Ni2(o- an- en)2Ce(NO3)2](NO3) [Güngö & Kose, 2017], ([NiLGd(NO3)3] and [NiLDy(NO3)3] (H2L = N,N′-bis(3-me hoxysalicylidene) cyclohexane-1,2-diamine), [Wen e al., 2015]) (Tab. 5.3.3). The Ln–Cl bond dis ances in 13 a e om he ange o 2.717(2) – 2.802(2) Å [2.630(3) – 2.714(3) Å o 14 and 2.6005(10) – 2.6955(9) Å o 15], which can be compa ed o he a e age Ce–Cl dis ance o 2.7467 Å (2.6829 Å o Gd–Cl and 2.6357 Å o Dy–Cl) ound in he CSD [Allen e al., 1994]. Table 5.3.3 Selec ed bond leng hs in Ni-Ln complexes 13, 14, 15, [Ni2(o- an- en)2Ce(NO3)2](NO3) (a) [Güngö & Kose, 2017], [NiLGd(NO3)3] (b) and [NiLDy(NO3)3] (c) [Wen e al., 2015]. 13 14 15 a b c Ni1–O2 1.843 (5) 1.842 (7) 1.843 (2) 1.876 (15) 1.851 (9) 1.807 (19) Ni1–O3 1.843 (5) 1.833 (7) 1.842 (2) 1.843 (16) 1.856 (9) 1.842 (18) Ni1–N1 1.827 (6) 1.816 (9) 1.834 (3) 1.82 (2) 1.840 (12) 1.89 (2) Ni1–N2 1.829 (7) 1.825 (9) 1.836 (3) 1.84 (2) 1.852 (10) 1.91 (2) Ln1–O1 2.710 (5) 2.658 (7) 2.654 (2) 2.835 (17) 2.525 (8) 2.47 (2) Ln1–O2 2.485 (5) 2.396 (7) 2.364 (3) 2.539 (13) 2.365 (9) 2.309 (16) Ln1–O3 2.469 (5) 2.385 (7) 2.343 (2) 2.544 (15) 2.398 (9) 2.361 (19) Ln1–O4 2.697 (5) 2.650 (7) 2.648 (2) 2.96 (2) 2.530 (8) 2.441 (16) 94 The e a e ou dinuclea molecules pe uni cell o 13 (and likewise o 14 and 15). The packing o he complex molecules is go e ned by medium-s eng h hyd ogen bonds o he O-HCl ype yielding a chain-like sup amolecula s uc u e unning along he a axis wi h addi ional, weake Ca –HCl, Cimine–HCl ype hyd ogen bonds and weak π-π s acking in e ac ions o he a oma ic ings o he neighbou ing chains o ming sup amolecula laye s in he ab plane (Fig. 5.3.2b), Tab. 5.3.4). The e a e only close con ac s o he C-HCl ype be ween planes, in ol ing me hyl and me hylene g oups o he ligand. a) b) Figu e 5.3.2 a) Molecula s uc u e o 13 along wi h i s a om numbe ing scheme. The he mal ellipsoids o non-hyd ogen a oms a e d awn a he 50 % p obabili y le el. b) C ys al s uc u e o 13. The ab plane is shown. Hyd ogen bonds and π-π s acking in e ac ions a e d awn as o ange and blue dashed lines, espec i ely. Ca bon a oms a e d awn in s ick model and H-a oms no in ol ed in hyd ogen bonding a e no shown o cla i y. 95 Table 5.3.4 Po en ial hyd ogen bonds in 13 – 15. D–H···A D–H [Å] H···A [Å] D···A [Å] D–H···A [°] Complex 13 O5-H1W∙∙∙Cl3i 0.845 (11) 2.32 (3) 3.122 (5) 157 (7) O5-H2W∙∙∙Cl2i 0.842 (11) 2.35 (3) 3.125 (5) 154 (6) C11-H11∙∙∙Cl2ii 0.93 2.65 3.577(8) 178.9 Complex 14 O5-H1W∙∙∙Cl3i 0.85 2.36 3.146 (7) 155.0 O5-H2W∙∙∙Cl2i 0.88 2.34 3.147 (8) 152.8 C11-H11∙∙∙Cl2ii 0.95 (10) 2.63 (10) 3.572 (13) 173 (9) Complex 15 O5-H1W∙∙∙Cl3i 0.836 (10) 2.363 (18) 3.149 (3) 157 (3) O5-H2W∙∙∙Cl2i 0.836 (10) 2.39 (2) 3.148 (3) 151 (3) C11-H11∙∙∙Cl2ii 0.93 2.63 3.562 (4) 176.9 π···π Cg···Cg [Å] α [°] β [°] γ [°] Slippage [Å] Complex 13 Cg1···Cg2iii 3.619 (5) 2.5 (4) 19.6 19.9 1.211 Complex 14 Cg1···Cg2iii 3.630 (7) 3.5 (5) 21.6 22.5 1.336 Complex 15 Cg1···Cg2iii 3.665 (2) 3.50 (17) 22.4 23.5 1.398 Symme y codes: i: 1 + x, y, z; ii: –1/2 – x, 1/2 + y, 1/2 – z; iii: 3/2 – x, –1/2 + y, 3/2 – z. Cg1 is he cen e o g a i y o he a oma ic ing o med by C2 – C7 a oms; Cg2 is he cen e o g a i y o he a oma ic ing o med by C12 – C17 a oms. [Ni2(o- an-en)2Ce2Cl6] (16) The molecula s uc u e o 16 is o med by he neu al dime ic complex molecule [Ni2(o- an-en)2Ce2Cl6] (Fig. 5.3.3a). In he monome ic uni , he Schi base ligand (o- an-en)2- p o ides wo coo dina ion si es – he inne , smalle ca i y is occupied by nickel(II) wi h squa e-plana coo dina ion o ming an {NiN2O2} ch omopho e; and he ou e , la ge coo dina ion si e accommoda es he ce ium(III) cen al a om su ounded by ou oxygen a oms o he ligand and h ee chlo ido ligands. The second monome ic uni is ela ed by he cen e o symme y [i: 1 – x, 1 – y, 1 - z]. 96 Monome ic uni s a e linked by wo µ-chlo ido ligands (Cl3 and Cl3i) whi h a Ce∙∙∙Ce dis ance in he dime o 4.5232 (3) Å. The Ni–O, Ni–N, Ce–O and Ce–Cl bond dis ances we e compa ed wi h hose ound in 20, [Ni2(o- an-en)2Ce(NO3)2](NO3) and [NiLDy(NO3)3] (H2L = N,N′-bis(3-me hoxysalicylidene)cyclohexane-1,2-diamine), [Güngö & Kose, 2017; Wen e al., 2015] (Tab. 5.3.5). Table 5.3.5 Selec ed bond leng hs in 16, 20, [Ni2(o- an-en)2Ce(NO3)2](NO3) (a) [Güngö & Kose, 2017] and [NiLDy(NO3)3] (b) [Wen e al., 2015]. 16 20 a b Ni1–O2 1.857 (2) 1.838 (9) 1.876 (15) 1.807 (19) Ni1–O3 1.849 (2) 1.841 (10) 1.843 (16) 1.842 (18) Ni1–N1 1.841 (3) 1.830 (12) 1.82 (2) 1.89 (2) Ni1–N2 1.839 (3) 1.830 (12) 1.84 (2) 1.91 (2) Ln1–O1 2.687 (2) 2.592 (9) 2.835 (17) 2.47 (2) Ln1–O2 2.499 (2) 2.332 (10) 2.539 (13) 2.309 (16) Ln1–O3 2.455 (2) 2.349 (10) 2.544 (15) 2.361 (19) Ln1–O4 2.676 (2) 2.572 (9) 2.96 (2) 2.441 (16) Ln1–Cl1 2.7586 (9) 2.730 (4) – – Ln1–Cl2 2.7334 (10) 2.605 (5) – – Ln1–Cl3 2.8534 (9) 2.636 (4) – – Hyd ogen bonding in e ac ions play an impo an ole in c ys al packing in 16. The p opaga ion o he hyd ogen bonding in e ac ion o he imine g oup C8–H8 and he Cl1ii chlo ine a om o ms a sup amolecula chain along he c axis (Fig. 5.3.3b), Tab. 5.3.6). The dis ance be ween Ce(III) a oms in neighbou ing dime s is 8.9361 (2) Å. The e a e no classical π-π s acking in e ac ions wi h Cg···Cg dis ance smalle han 5 Å and nei he do any classical C–H···π in e ac ions con ibu e o he c ys al packing. On he o he hand, he dis ance o 3.501 Å be ween he cen al Ni1 a om and he cen e o g a i y o he a oma ic ing o med by ca bon a oms om C2ii o C7ii is a he sho and can be conside ed as ing-me al in e ac ion (symme y code: ii: 1 – x, 1 – y, – z). The line h ough Ni1 and he Cgii cen e o g a i y de ia es only 7.65° om he no mal o he equa o ial plane o Ni1 composed o O3, O2, N1 and N2. This in e molecula in e ac ion links dime ic molecules in o he sup amolecula chain along he c axis (Fig. 97 5.3.3b) which is suppo ed only by he hyd ogen bonding in e ac ion men ioned be o e. Sup amolecula 3D s uc u e is hen o med by o he close con ac s o he C–H···Cl ype. a) b) Figu e 5.3.3 a) The molecula s uc u e o 16 along wi h i s a om numbe ing scheme. The second pa o he dime gene a ed by he cen e o symme y is d awn wi h ligh colou s o cla i y. The he mal ellipsoids o non-hyd ogen a oms a e d awn a he 50 % p obabili y le el. b) C ys al s uc u e o 16. The bc plane is d awn. Hyd ogen bonds and π-π s acking in e ac ions a e d awn as o ange and blue dashed lines, espec i ely. 98 Table 5.3.6 Po en ial hyd ogen bonds and ing-me al in e ac ion in 16. D–H···A D–H [Å] H···A [Å] D···A [Å] D–H···A [°] C8–H8···Cl1ii 0.97 (4) 2.67 (4) 3.546 (4) 150 (3) π···M Cg···M [Å] M–Pe p [°] β [°] Cg1···Ni1ii 3.501 -3.408 13.20 Symme y code: ii: 1 – x, 1 – y, – z. Cg1 is he cen e o g a i y o he a oma ic ing o med by C2 – C7 a oms. [Ni(o- an-en)DyCl3] (17) and [Ni(o- an-en)DyCl3]·E OH (18) The molecula s uc u e o bo h complexes 17 and 18 consis s o bime allic complex molecules [Ni(o- an-en)DyCl3] wi h he nickel(II) cen al a om in squa e plana coo dina ion by he Schi base ligand (o- an-en)2- and he dysp osium(III) cen al a om loca ed in he ou e coo dina ion si e o he ligand. The coo dina ion sphe e o Dy(III) is hen comple ed by h ee chlo ido ligands (Figs. 5.3.4a) and 5.3.5a). Addi ionally, he asymme ic uni o 18 possesses an e hanol sol a e molecule a ached o he complex by a hyd ogen bonding in e ac ion o he O–H···Cl ype. The Ni–O, Ni– N and Dy–O dis ances a e lis ed in Table 5.3.7, compa ed wi h hose ound in [NiLDy(NO3)3] (H2L = N,N′-bis(3-me hoxysalicylidene)cyclohexane-1,2-diamine), [Wen e al., 2015]. The Dy–Cl bond dis ances a e in line wi h he a e age alue o 2.6357 Å o Dy–Cl bond leng hs ound in he CSD [Allen e al., 1994]. The complex [Ni(o- an-en)DyCl3] (17) c ys allizes in iclinic space g oup P-1. I s c ys al s uc u e is held by weake hyd ogen bonds o he C–H···Cl ype o ming sup amolecula chains along he a axis. The hyd ogen bonding sys em is suppo ed by π-π s acking in e ac ions be ween he neighbou ing a oma ic ings o med by C12 – C17, also along he a axis (Fig. 5.3.4b). The 3D packing is hen held by weake in e molecula in e ac ions and close con ac s. Complex 18 c ys allizes in monoclinic space g oup P21/c. I s c ys al s uc u e is buil up o complex [Ni(o- an-en)DyCl3] uni s and E OH sol a e molecules which a e linked oge he by hyd ogen bonding in e ac ions o he O–H···Cl, C–H···O and C– H···Cl ypes (Tab. 5.3.9). The c ys al packing is hen suppo ed by in e molecula in e ac ions o he a oma ic ings be ween each o he and in e ac ion o he π sys em o he a oma ic ing o med by C12 – C17 and he Ni1 cen al a om (Tab. 5.3.9, Fig. 5.3.5b). 99 Table 5.3.7 Selec ed bond dis ances in 17, 18 and [NiLDy(NO3)3] (a) [Wen e al., 2015]. 17 18 a Ni1–O2 1.832 (5) 1.8536 (17) 1.807 (19) Ni1–O3 1.858 (5) 1.8466 (16) 1.842 (18) Ni1–N1 1.822 (7) 1.838 (2) 1.89 (2) Ni1–N2 1.835 (7) 1.837 (2) 1.91 (2) Dy1–O1 2.481 (5) 2.5136 (7) 2.47 (2) Dy1–O2 2.305 (5) 2.3165 (17) 2.309 (16) Dy1–O3 2.320 (5) 2.3163 (16) 2.361 (19) Dy1–O4 2.528 (5) 2.4987 (17) 2.441 (16) Dy1–Cl1 2.566 (2) 2.5986 (7) – Dy1–Cl2 2.6015 (19) 2.6222 (6) – Dy1–Cl3 2.625 (2) 2.6071 (7) – Table 5.3.8 Po en ial hyd ogen bonding and π-π s acking in e ac ions in 17. D–H···A D–H [Å] H···A [Å] D···A [Å] D–H···A [°] C11–H11···Cl3i 0.95 2.75 3.654 (8) 158 C13–H13···Cl1ii 0.95 2.80 3.571 (8) 139 π···π Cg···Cg [Å] α [°] β [°] γ [°] Slippage [Å] Cg1···Cg1ii 3.535 (4) 0.0 (4) 15.8 15.8 0.965 Symme y codes: i: 1 – x, 1 – y, 1 – z; ii: 2 – x, 1 – y, 1 – z. Cg1 is he cen e o g a i y o he a oma ic ing o med by C12 – C17. Table 5.3.9 Po en ial hyd ogen bonding, π-π s acking and ing-me al in e ac ions in 18. D–H···A D–H [Å] H···A [Å] D···A [Å] D–H···A [°] O5–H5W···Cl2 1.09 (7) 2.31 (7) 3.293 (3) 150 (5) C8–H8···O5i 0.95 2.57 3.458 (4) 155 C11–H11···Cl1ii 0.95 2.75 3.643 (3) 157 π···π Cg···Cg [Å] α [°] β [°] γ [°] Slippage [Å] Cg1···Cg1iii 3.8727 (15) 0.0 (12) 27.5 27.5 1.788 Cg1···Cg2i 3.8021 (16) 8.65 (13) 22.7 16.9 1.466 100 Table 5.3.9 Con inued. π···M Cg···M [Å] M–Pe p [°] β [°] Cg2···Ni1ii 3.875 -3.360 29.88 Symme y codes: i: x, 1/2 – y, 1/2 + z; ii: 1 – x, 1 – y, 1 – z; iii: 2 – x, – y, 1 – z; i : x, – 1 + y, z. Cg1 is he cen e o g a i y o he a oma ic ing o med by C2 – C7; Cg2 is he cen e o g a i y o he a oma ic ing o med by C12 – C17. Pa ame e s α, β and γ a e de ined as in Pla on. a) b) Figu e 5.3.4 a) The molecula s uc u e o 17 along wi h i s a om numbe ing scheme. The second pa o he diso de ed g oup is d awn wi h ligh colou s o cla i y. The he mal ellipsoids o non-hyd ogen a oms a e d awn a he 50 % p obabili y le el. b) C ys al s uc u e o 17. The sup amolecula chain along he a axis is d awn. Hyd ogen bonds and π-π s acking in e ac ions a e d awn as o ange and blue dashed lines, espec i ely. Ca bon a oms a e d awn in s ick model and H-a oms no in ol ed in hyd ogen bonding a e no shown o cla i y. 107 he ini ial p oduc [He el, 1931; Lo ge ing, 1959]. The explana ion o he symme y ela ion be ween ini ial and inal p oduc lies in he p ocess o nuclea ion which is he con olling ac o o opo ac ic eac ions. Nuclei (o he changed c ys al) a e o med in he ma ix o he o iginal c ys al. Gene ally, nuclei ha ha e he app op ia e o ien a ion ha e a highe p obabili y o being o med and o con inue o g ow. As a esul , he o ien a ion o opo ac ic ex u e a ises om he o ien a ion o nuclei o c ys alliza ion which is de e mined by he ma ix o he ini ial c ys al. Howe e , i is impo an o no e ha bo h c ys al s uc u es a e di ec ionally ela ed bu he e is no need o a c ys allog aphic g oup-subg oup ela ionship be ween he ini ial and inal p oduc . Howe e , he e a e also such ela ed sys ems and also, he e a e cases when he o iginal space g oup is e ained. 5.3.1.1 C ys alline ans o ma ion I: opo ac ic eac ion Now, le ’s see he i s c ys alline ans o ma ion in his wo k – he opo ac ic eac ion o [Ni(o- an-en)DyCl3(H2O)] Fo m II (19) yielding he complex [Ni2Dy2(o- an-en)2Cl6] (20). Wi h he de ailed look on he sup amolecula dime ic s uc u e o 19, we p edic ed he possibili y o o cing he dysp osium(III) complex o became a dime ic e anuclea one. The sup amolecula dime o 19 seems o be co ec ly disposed o enable he o ma ion o he dime a e dehyd a ion. The p edic ion was con i med by a se ies o expe imen s on he single-c ys al X- ay di ac ome e . Di ac ion da a we e measu ed using one single-c ys al sample a se e al empe a u es, wi h he empe a u e being aised in s eps (Tab. 5.3.1.1.1). We s a ed wi h p e-expe imen I a a empe a u e o 277 K, eco ded he uni cell pa ame e s and hen began o aise he empe a u e slowly in se e al s eps. We obse ed he olume o he uni cell inc easing wi h ising empe a u e; see p e-expe imen s I – IV in he able. We s opped asing he empe a u e when he uni -cell olume s opped inc easing (p e- expe imen V) and le he c ys al a ha empe a u e, T = 357 K (on i s Mi egen moun , on he di ac ome e , in he ni ogen cu en ) while we moni o ed he uni cell changes (p e-expe imen s VI – VIII). A ha poin we collec ed a ull se o di ac ion da a. We obse ed a sligh dec ease in he uni -cell olume; see he ull da a collec ion IX. The analysis o he c ys al s uc u e o IX con i med ou p e ious conjec u e and e ealed he new c ys al s uc u e. Chemically, he complex [Ni(o- an-en)DyCl3(H2O)] (Fo m II, 108 19) had been dehyd a ed and had dime ized o o m [Ni2(o- an-en)2Dy2Cl6] (20) while e aining i s single c ys al cha ac e (Fig. 5.3.1.1.1). Table 5.3.1.1.1 E olu ion o he uni cell pa ame e s o he sample 19 while a ying he empe a u e. Exp. No. I (p e) II (p e) III (p e) IV (p e) T [K] 277 307 332 347 a [Å] 13.494 (6) 13.514 (6) 13.534 (7) 13.548 (7) b [Å] 9.379 (4) 9.412 (4) 9.422 (4) 9.425 (5) c [Å] 17.213 (9) 17.199 (11) 17.193 (12) 17.205 (12) β [°] 91.19 (4) 91.25 (5) 91.25 (5) 91.16 (5) V [Å3] 2178 (2) 2187 (2) 2192 (2) 2197 (2) Exp. No. V (p e) VI (p e) VII (p e) VIII (p e) T [K] 357 357 357 357 a [Å] 13.555 (8) 13.538 (8) 13.555 (16) 13.529 (18) b [Å] 9.430 (5) 9.444 (5) 9.422 (8) 9.437 (8) c [Å] 17.191 (12) 17.198 (12) 17.206 (12) 17.21 (2) β [°] 91.12 (6) 91.19 (7) 90.81 (11) 90.72 (11) V [Å3] 2197 (2) 2198 (2) 2197 (3) 2197 (5) Exp. No. IX (FD) X (p e) XI (FD) T [K] 357 223 223 a [Å] 12.095 (2) 12.078(8) 12.0999(11) b [Å] 9.4280 (11) 9.409(6) 9.4050 (4) c [Å] 18.642 (3) 18.53(2) 18.5619(14) β [°] 92.561 (13) 91.60(9) 91.754 (7) V [Å3] 2123.7 (6) 2105(3) 2111.3 (3) p e = p e-expe imen , FD = ull da a 109 a) b) c) d) Figu e 5.3.1.1.1 a) The sup amolecula dime in [Ni(o- an-en)DyCl3(H2O)] (Fo m II, 19). b) The molecula s uc u e o [Ni2(o- an-en)2Dy2Cl6] (20). The compa ison o he c ys al s uc u es o 19 (a) and 20 (b). In o de o see i he “changed” c ys al s uc u e was s able, we lowe ed he empe a u e o 223 K and collec ed da a again (see p e-expe imen X and da a collec ion XI in Tab. 5.3.1.1.1). The new c ys al s uc u e was e ained and he c ys al did no collapse a e he hea ing, eac ion and cooling down p ocesses. To sum up, we conduc ed h ee such expe imen s wi h h ee di e en single c ys als o 19 and we obse ed he same beha iou . Tha p o es ha his eac ion is no in e mi en o o ui ous bu a he is an in insic p ope y o he compound in he c ys alline s a e. We no e ha a e ou las expe imen , he “changed” c ys al was emo ed om he ni ogen cu en and exposed o he ambien condi ions o he labo a o y a oom empe a u e o abou 6 hou s. A e ha ime, he same c ys al was 110 again pu in o he ni ogen cu en a 173 K and ixed o he di ac ome e . The esul ing ull s uc u e analysis e ealed he backwa d change om he e anuclea s uc u e o [Ni2(o- an-en)2Dy2Cl6] (20) o he dinuclea s uc u e o [Ni(o- an- en)DyCl3(H2O)] Fo m II (19). A de ailed look a he o ien a ion o he molecules o he inal p oduc e eals he ela ion be ween he ini ial and inal c ys al s uc u es (Fig. 5.3.1.1.1c),d). The elease o wa e molecules ga e ise o he mo ion o he sup amolecula dime s close o each o he and he o ma ion o he wo chlo ide b idges. This p ocess can be classi ied as a opo ac ic eac ion. On he o he hand, he o ien a ion o he wo uni cells is no in a line. Following he speci ic ules o opo axy, i is impo an o use a cell se ing o he inal p oduc ha is ela ed o ha o he p ecu so . In he p esen case, ha impe a i e ob ia es he use o wha would o he wise be he con en ional cell. Speci ically he p ecu so - ela ed cell se ing o he inal p oduc is monoclinic wi h be a < 90º. The ans o ma ion om he di ac ome e -selec ed "s anda d cell" o he opo ac ic p oduc cell is as ollows: (𝑎´ 𝑏´ 𝑐´)∙(−1 0 0 0 −1 0 0 0 1)=(𝑎 𝑏 𝑐) whe e a´, b´, c´ a e he uni cell pa ame e s gi en by he da a collec ion p og am and a, b, c a e he co ec ed uni cell pa ame e s. The inal uni cell pa ame e s a e collec ed up in Tab. 5.3.1.1.2. Table 5.3.1.1.2. The ini ial and inal uni cell pa ame e s o he opo ac ic change. [Ni(o- an-en)DyCl3(H2O)] (19) [Ni2(o- an-en)2Dy2Cl6] (20) T [K] 173 173 a [Å] 13.4168 (3) 12.118 (3) b [Å] 9.3666 (2) 9.3732 (9) c [Å] 17.2733 (4) 18.545 (3) β [°] 91.377 (2) 88.535 (16) V [Å3] 2170.11 (9) 2105.7 (6) Now, we can see ha he opo ac ic eac ion esul ed in he educ ion o he uni cell size and he monoclinic angle β dec eased o a alue smalle han 90° (Tab. 5.3.1.1.2). 111 I is ins uc i e o look a he X- ay di ac ion pa e ns aken du ing he p ocess o opo axy. The opo ac ic eac ion happens h oughou he whole olume o he c ys al only a ely and o en we can see bo h phases, ini ial and p oduc s uc u es in he di ac ion pa e n a he same ime. A i s glance, his can be obse ed in ecip ocal- la ice econs uc ions (“p ecession pho os” in popula e minology) o he “changed” s uc u e o 20 and he es o ed s uc u e o 19 a e one ull cycle o he opo ac ic eac ion (Fig. 5.3.1.1.2). Ne e heless, we ha e no ound he p esence o bo h s uc u es in c ys al space. Figu e 5.3.1.1.2. P ecession pho ogaphs o he 0kl, h0l and hk0 laye s (le o igh ) om he da a o [Ni2(o- an-en)2Dy2Cl6] (20) ( op) and es o ed [Ni(o- an-en)DyCl3(H2O)] (19) (bo om) measu ed a 173 K. Wha we see in h0l can be explained in e ms o he la ge mosaic ha is gene a ed as a esul o s ain h oughou he c ys al caused by he change in he uni cell. The p ecession pho og aphs o he 0kl and hk0 laye s look clean wi h he di ac ion spo s well shaped. On he o he hand, he h0l laye shows mosaic di ac ion spo s. Dispa i y o di ec ions indica es i s o igin in symme y. The mosaic is no ha well isible on he 0kl and hk0 laye s, as he bigges di e ence in uni cell pa ame e s is in he alues o a, c and β and hey a e all included in he p ecession pho og aph o he h0l laye . The ac ha he c ys al s uc u es o he wo e anuclea complexes [Ni2Ln2(o- an-en)2Cl6] (Ln = Ce in 16 and Dy in 20) a e no isos uc u al is a 112 consequence o hei ha ing been p epa ed by wo di e en syn he ic pa hways (Scheme 5.3.1). While he ce ium(III) complex 16 o med he c ys al s uc u e wi h he lowes ene gy ollowing a eac ion wi h 13 in e hanol as a s a ing poin , he dysp osium(III) sample needed he ans o ma ion h ough he in e media e s uc u e 19 ollowed by opo ac ic eac ion o ced by hea ing he sample. I is impo an o conside he mechanism o opo ac ic change in he c ys al s uc u e wi h a de ailed look a he opochemical pos ula e ha eac ion in he solid s a e occu s wi h a minimum o a omic o molecula mo emen [Cohen & Schmid , 1964]. The pos ula e says e y clea ly ha solid-s a e eac ions a e con olled by he es ic ed dis ances and he e o e, he c ys al packing canno be u he s abilized a e dime iza ion. 5.3.1.2 C ys alline ans o ma ion II: Obse ed in powde di ac ion pa e n The s udy o c ys alline ans o ma ion o he se ies o [Ni(o- an- en)LnCl3(H2O)] (Ln = Ce, Gd and Dy) can be e y ich as he e a e se e al di e en e ec s o dehyd a ion in he solid s a e o in he dissol ed o m. The las a ian we s udied was he dehyd a ion o [Ni(o- an-en)DyCl3(H2O)] (Fo m I, 15) in he solid s a e. We obse ed he opo ac ic ans o ma ion o he complex by hea ing he powde sample and collec ing he powde di ac ion da a a se e al empe a u e s eps: RT, 80°C, 100°C, 120°C, 140°C, 160°C, RT. The sample emained 30 mins a each s ep up o 160°C. The whole p ocess o c ys alline changes, as obse ed h ough he powde di ac ion pa e ns, is pic u ed below. Wi h e e ence o he powde pa e ns s a ing om RT and eaching 120°C, he c ys alline phase o he sample is s able. The i s change comes a 140°C whe e we can see he p e ious phase p esen along wi h he addi ional peaks o he new phase. The pa e n clea s up a 160°C whe e we no longe see he ini ial phase bu only he “changed” phase is obse ed. This phase is clea ly p esen also a e cooling he sample down. The e e se p ocess was obse ed upon keeping he sample a ambien condi ions o a longe ime. A e keeping he sample a RT o e he se e al days (weekend), we collec ed he powde di ac ion da a again which showed ha he c ys al s uc u e had changed back o he ini ial complex [Ni(o- an-en)DyCl3(H2O)] (Fo m I) and he sample was s ill c ys alline. A e his eco e y, he same sample was kep in a humid a mosphe e and a e se e al mo e days, he powde di ac ion da a collec ion showed he hi d phase. 113 We plan o conduc a single-c ys al X- ay di ac ion s udy o hese phase changes. Figu e 5.3.1.2.1. The powde di ac ion pa e ns o [Ni(o- an-en)DyCl3(H2O)] (Fo m I, 15) changing a a ious empe a u es and ime. 114 5.3.2 Magne ic p ope ies o he [Ni(o- an-en)LnCl3(H2O)] isos uc u al amily Re u ning o compounds 13-15, he powde samples we e examined o hei magne ic p ope ies. Be o e he measu emen s, he samples we e s ic ly pu i ied and hei pu i y was checked by X- ay powde di ac ion analysis. The esul s o he powde di ac ion da a we e compa ed wi h he da a ob ained om single-c ys al X- ay di ac ion analysis o 13-15 p o ided a oom empe a u e applying LeBail e inemen and using he p og am Jana2006 [Le Bail e al., 1988; Le Bail, 2005; Pe říček e al., 2014]. Fo he e inemen , he Pseudo-Voig me hod was used. The Gaussian pa ame e s o basic b oadening by sli s (U), wa e leng h dispe sion (V) and in luence o monoch oma o (W) we e eely e ined while he pa ame e o Sche e coe icien o Gaussian b oadening (P) was no e ined in he calcula ions. F om he Lo en zian pa o he e inemen , he pa icle b oadening was e ined. The asymme y o peaks was e ined using he Bé a -Baldinozzi co ec ion me hod wi h 4 e ms, all o hem eely e ined. Backg ound was co ec ed using Legend e polynomials (10 – 18 e ms) and sligh ly shi ed (shi pa ame e e ined). The e inemen s a e shown in Fig. 5.3.2.1 and he inpu and e ined uni cell pa ame e s and alues o R(p), R(wp) and GooF o he e inemen o all h ee samples a e lis ed in Tab. 5.3.2.1. Table 5.3.2.1 The inpu and e ined uni cell pa ame e s and alues o R(p), R(wp) and GooF o samples 13, 14 and 15, espec i ely. 13 14 15 Inpu da a: a [Å] 7.1269 (3) 7.0236 (3) 7.00940 (10) b [Å] 14.4698 (6) 14.3753 (9) 14.3916 (3) c [Å] 21.0732 (12) 20.9662 (13) 20.9556 (5) β [°] 91.377 (2) 92.216 (9) 91.833 (2) Re ined da a: a [Å] 7.119 (13) 7.023 (3) 7.0128 (9) b [Å] 14.46 (3) 14.381 (6) 14.4023 (19) c [Å] 21.02 (4) 20.901 (9) 20.985 (3) β [°] 92.741 (6) 92.173 (6) 91.803 (4) R(p) 0.0396 0.0490 0.0457 R(wp) 0.0544 0.0690 0.0616 GooF 1.52 1.65 1.69 115 Figu e 5.3.2.1 LeBail e inemen o he measu ed powde di ac ion pa e ns o complexes 13, 14 and 15, espec i ely. Red line ep esen s he e ined pa e n; blue line ep esen s measu ed da a; black line ep esen s he di e ence. 116 A e he ho ough pu i ica ion and e i ica ion o he pu i y o all h ee samples, he DC and AC magne ic da a we e collec ed in o de o s udy hei magne ic p ope ies. Fi s ly, he DC da a will be commen ed he e in his wo k. We would like o no e ha all he magne ic da a collec ion and e alua ion was done by he g oup o p o . Boča om he Uni e si y o Ss. Cy il and Me hodius in T na a. The c ys al s uc u es o 13, 14 and 15 show he Ni(II) cen al a om o be in a squa e plana en i onmen o med by ou oxygen dono a oms. Thus, i is magne ically silen , excep o some empe a u e-independen magne ism a ising om he p esence o low-lying exci ed s a es. On he o he side, he lan hanide Ln(III) cen es possess o bi al and spin angula momen um and he g ound mul iple is 2F5/2 o Ce(III), 8S7/2 o Gd(III) and 6H15/2 o Dy(III), wi h he magne ogy ic a ios gJ = 6/7, 2 and 4/3, espec i ely. Thus, he magne iza ion pe o mula uni should sa u a e o M1 = Mmol/(NAμB) = gJ·J = 6/7 × 5/2 = 15/7, 2 × 7/2 = 7, and 4/3 × 15/2 = 10. The high empe a u e limi o he e ec i e magne ic momen , based upon he magne ic suscep ibili y, is μe /μB = gJ[J(J + 1)]1/2 = (6/7)(5/2 × 7/2)1/2 = 2.54, 2 × (7/2 × 9/2)1/2 = 7.94, and (4/3) (15/2 × 17/2)1/2 = 10.6, espec i ely. The DC magne ic da a o 13 a e shown in Fig. 5.3.2.2a). Clea ly isible linea dependence o he e ec i e magne ic momen be ween T = 9–300 K indica es some empe a u e-independen pa amagne ism as expec ed o he Ni(II) cen e in a squa e plana en i onmen : χTIP = 6 × 10−9 m3 mol−1. The oom- empe a u e e ec i e magne ic momen ( he high- empe a u e limi ) adop s a alue o μe = 2.36μB, ha is no a om he single ion alue (2.54). The magne iza ion da a a T = 2.0 and B = 7 T, M1 = 1.0, is much lowe ela i e o isola ed mul iple 2F5/2 o Ce(III) (2.1). Owing o he e ec o he c ys al ield, he six- old degene a e g ound a omic mul iple 2F5/2 is spli in o h ee c ys al- ield mul iple s (K ame s double s). The magne ic da a was i ed assuming ha only he lowes K ame s double is he mally popula ed. 123 5.4 Benzoic acid as O-dono ligand – conse ing he oxida ion s a e o Co(II) Resea ch in o he magne ism o Co(II) complexes has yielded a numbe o unexpec ed esul s in ecen imes. Gene ally speaking, hese sys ems possess a e y high magne ic aniso opy ha g ows in he se ies o e a-, pen a- and hexacoo dina e complexes [C aig & Mu ie, 2015; Gómez-Coca e al., 2015; F os e al., 2016]. Due o he ac ha we we e no able o conse e he oxida ion s a e +II o cobal complexes using ou selec ed Schi base ligand we ied a di e en app oach, namely using a ligand which is s ic ly an O-dono – benzoic acid. The ihyd a e o cobal (II) benzoa e (21) in single c ys al o m was p epa ed by he di ec eac ion o cobal (II) ca bona e wi h benzoic acid in boiling wa e ollowed by c ys alliza ion. We no e ha se e al al e na i es o cobal (II) benzoa e we e p epa ed using di e en syn he ic and c ys alliza ion condi ions, namely wo di e en polymo phs o anhyd ous o m [Sisquei a e al., 2007; Spohn & S ähle, 1988; Ga ilenko e al., 2005], dihyd a e [Eph aim & P is e , 1925] and e ahyd a e o m [Eph aim & P is e , 1925; Bala ew e al., 1985]. The esul ing single c ys als o 21 we e cha ac e ized chemically and spec oscopically. The c ys al s uc u e o 21 is ionic, composed o posi i ely cha ged [Co(Bz)(H2O)2]nn+ chains, benzoa e anions and s oichiome ically one sol a e wa e molecule (Fig. 5.4.1). The same ype o c ys al s uc u e was epo ed o he isos uc u al Ni(II) analogue [V áblo á e al., 2016] and o he simila Cu(II) complex which, howe e , c ys allizes in a di e en space g oup [Koizumi e al., 1963]. The chains in 21 a e o med by Co(II) a oms iply b idged by wo μ2-aqua ligands and one syn–syn benzoa o b idge. Due o he iple b idging, neighbou ing Co(II) a oms a e ela i ely close o each o he , wi h a Co⋯Co dis ance o 3.1159(2) Å; his alue is longe han he co esponding Ni⋯Ni sepa a ion o 3.0671(1) Å in he isos uc u al nickel complex [V áblo á e al., 2016]. Somewha longe Co⋯Co dis ances we e ound in he monoclinic (3.145(1) Å) and o ho hombic (3.1657(4) and 3.1957(4) Å) o ms o anhyd ous cobal (II) benzoa e [Spohn & S ähle, 1988; Ga ilenko e al., 2005]. 124 Figu e 5.4.1 One segmen o he s uc u e o 21 displaying he coo dina ion mode o wo iply b idged Co(II) a oms and benzoa e anions along wi h he a om numbe ing scheme. Displacemen ellipsoids a e d awn a he 50% p obabili y le el. Symme y codes: i: 0.5 − x, y, − z; ii: 0.5 + x, 1 − y, z; iii: 1 − x, 1 − y, − z; i : 1.5 − x, y, − z; : 1 + x, y, z; i: 0.5 − x, y, 1 − z. Al e na i ely, he chains in 21 can be iewed as o med o {CoO6} oc ahed a wi h common edges; neighbou ing oc ahed a a e can ed (Fig. 5.4.2) wi h an angle o 26.27° be ween he Oax–Co–Oax ec o s in he adjacen oc ahed a. In he hyd a e complex 21 he cen al Co(II) a om occupies a special posi ion (cen e o in e sion) and is hexacoo dina ed [O2(benzoa e)O4(aqua) dono se ]. Compa ison o he axial Co–O bond o 1.9775(16) Å ( wice) wi h he mean equa o ial Co–O bond o 2.158(19) Å (Tab. 5.4.1) shows ha he coo dina ion polyhed on can be iewed as a e agonally comp essed oc ahed on, wi h he obse ed comp ession o he oc ahed on exp essed by he a io κ = (Co–O)ax/(Co–O)eq = 0.92. The neighbou ing chains in 21 a e in e connec ed, wi h he pa icipa ion o sol a e wa e molecules (O4 a oms) and benzoa e anions, by a he s ong hyd ogen bonds o he O–H⋯O ype wi h a mean O⋯O dis ance o 2.66(3) Å (Fig. 5.4.3, Tab. 5.4.2), o ming sup amolecula laye s. Table 5.4.1 Selec ed geome ic pa ame e s [Å, °] o 21. Co1–O1 1.9775 (16) O2–Co1–O2i 83.83 (7) Co1–O2 2.1418 (18) O2i–Co1–O2iii 96.17 (7) Co1–O2i 2.1745 (18) O1–Co1–O1iii 180 Co1–Co1i 3.1159 (2) Co1–O2ii–Co1i 92.42 (7) C1–O1 1.271 (2) O1–C1–O1i 124.5 (3) C6–O3 1.265 (2) O3–C6–O3 i 124.2 (3) Symme y codes: i: 0.5 − x, y, − z; ii: 0.5 + x, 1 − y, z; iii: 1 − x, 1 − y, − z; i : 1.5 − x, y, − z; : 1 + x, y, z; i: 0.5 − x, y, 1 − z. 125 Figu e 5.4.2 View o he posi i ely cha ged [CoBz(H2O)2]nn+ chain unning along he a axis wi h delinea ed polyhed a {CoO6}. Figu e 5.4.3 Hyd ogen bonding sys em in 21. Hyd ogen bonds a e d awn as o ange dashed lines. The bc plane is pic u ed. Table 5.4.2 Possible hyd ogen bonds [Å, °] o 21. D–H···A D–H [Å] H···A [Å] D···A [Å] D–H···A [°] O2–H2A···O3 0.85 (3) 1.79 (3) 2.630 (2) 170 (3) O2–H2B···O4 0.77 (3) 1.93 (3) 2.679 (2) 163 (3) O4–H4A···O3 ii 0.85 (3) 1.84 (3) 2.681 (2) 175 (3) Symme y code: ii: x – 0.5, -y + 1, z. 126 The iden i y and phase pu i y o he bulk sample was checked by powde X- ay di ac ion. The esul s o powde di ac ion da a we e compa ed wi h he da a ob ained om single-c ys al X- ay di ac ion analysis applying LeBail e inemen and using he p og am Jana2006 [Le Bail e al., 1988; Le Bail, 2005; Pe říček e al., 2014]. Fo he e inemen , he Pseudo-Voig peak-shape model was used. The Gaussian pa ame e s U, V and P we e eely e ined while he in luence o he monoch oma o (W) was no e ined in he calcula ions. Pa icle and s ain b oadening was i ed by using bo h, X and Y pa ame e s o he Lo en zian pa o he i ing peak-shape unc ion. The asymme y o peaks was e ined using he Bé a -Baldinozzi co ec ion me hod wi h 4 e ms, only he i s o hem eely e ined. Backg ound was co ec ed using Legend e polynomials (11 e ms). The e inemen is shown in Fig. 5.4.4 and he inpu and e ined uni cell pa ame e s and alues o R(p), R(wp) and GooF o he e inemen o all h ee samples a e lis ed in he Tab. 5.4.3. Figu e 5.4.4 Resul s o Le Bail e inemen o he powde di ac ion pa e n o 21. Red line ep esen s he e ined pa e n; blue line ep esen s measu ed da a; black line ep esen s he di e ence. 127 Table 5.4.3 The inpu and e ined uni cell pa ame e s and alues o R(p), R(wp) and GooF om he LeBail analysis o 21. Inpu Da a Re ined Da a a [Å] b [Å] c [Å] β [°] 6.2299 (4) 34.115 (3) 6.9101 (4) 95.689 (7) 6.202 (2) 34.287 (3) 7.0189 (10) 96.71 (3) R(p) R(wp) Goo 0.1929 0.2821 8.74 5.4.1 Magne ic p ope ies o 21 Based on he DC measu emen s, he e ec i e magne ic momen inc eases om i s oom- empe a u e alue o μe = 5.6μB o i s maximum μe = 15.9μB a T = 6.5 K; hen i d ops apidly o a alue o μe = 8.0μB a T = 1.9 K (Fig. 5.4.1.1). The mola magne ic suscep ibili y eaches a maximum on cooling and below 3.4 K i s ays cons an . These da a indica e a ansi ion o he pa amagne ic phase wi h exchange in e ac ions o a e omagne ic na u e o he an i e omagne ic phase a he Néel empe a u e TN = 5.5 K. The posi ion o his c i ical empe a u e sligh ly depends on he applied DC magne ic ield (BDC = 0.01 o 0.1 T). The highe empe a u e ail abo e he Néel empe a u e is una ec ed by he magne ic ield (Fig. 5.4.1.1b) and c). The equency dependence o he AC suscep ibili y componen s is p esen ed in Fig. 5.4.1.2. The da a show wo maxima in he χ″ s. cu e, indica ing wo elaxa ion channels. The onse o he low- equency (LF) mode is well isible in he ange T = 1.9 – 3.3 K. Abo e 3.9 K he ou -o -phase suscep ibili y is supp essed and hen he sample becomes a pa amagne . The high- equency (HF) b anch possesses i s maximum be ween 1 and 1000 Hz and i con inues abo e 1500 Hz. Bo h componen s o he AC suscep ibili y ha e been i ed simul aneously and a wo-se Debye model was applied in econs uc ing he AC suscep ibili y da a. The LF b anch a χ″ s a s g owing below 1 Hz and i s maximum lies ou side he limi s o he measu emen s −0.1 Hz. The e o e he elaxa ion ime is τ(LF) > 1.6 s o a se o low empe a u es i espec i e o he da a i ing ( his indica es ha τLF(2.1 K) = 14 s). The ou -o -phase suscep ibili y componen 128 o BDC = 0.1 T ises o i s maximum a T = 4.1 K and hen i a enua es apidly on u he hea ing. A TN > 4.7 K i is almos ze o because o he pa amagne ic phase. a) b) c) Figu e 5.4.1.1 DC magne ic da a o 21. a) E ec i e magne ic momen (inse : low empe a u e suscep ibili y da a); b, c) e ec i e magne ic momen and suscep ibili y da a aken a di e en ields. 129 Figu e 5.4.1.2 F equency dependence o he AC suscep ibili y componen s o 21. Full lines – calcula ed in e pola ion/ex apola ion and dashed – isual guide. A plo o he ou -o -phase e sus he in-phase componen o he AC suscep ibili y (Fig. 5.4.1.3, le ) is depic ed on an A gand diag am consis ing o wo o e lapping a cs. The elaxa ion imes de i ed om he da a i ing a e used o cons uc ing he A henius-like plo (Fig. 5.4.1.3, igh ). As a as he HF b anch is conce ned, wo elaxa ion egimes ope a e. The high- empe a u e one was analysed in e ms o he A henius equa ion τ = τ0 exp(U/kBT) whe e he ba ie o spin e e sal U and he ex apola ed elaxa ion ime τ0 appea . The linea i using h ee highe - empe a u e poin s ga e U/kB = 81.3 K and τ0 = 6.6 × 10−15 s. The low- empe a u e egime is domina ed by he Raman p ocess o which he elaxa ion ime ollows a powe -law equa ion τ−1 = CTn o ln τ = −ln C − n ln T. The linea eg ession ga e C = 130 1.5 × 10−3 s−1 K−n and n = 12.1. The ull da a se was i ed wi h a join elaxa ion equa ion τ−1 = τ0 −1 exp(−U/kBT) + CTn which ga e U/kB = 88.7 K, τ0 = 1.2 × 10−15 s, and C = 1.4 × 10−3 s−1 K−12 o n = 12. These da a we e used o econs uc ing he in e pola ion and ex apola ion line in he cu ed A henius-like plo . Figu e 5.4.1.3 A gand diag am – le , and he A henius-like plo – igh o 21 a BDC = 0. Dashed s aigh lines – i o a limi ed da a se . Non-linea cu e – a i o he ull da a se . 131 6 Conclusions In conclusion, a se ies o no el Ni(II) and Co(II) compounds as well as bime allic 3d-4 complexes using selec ed N,O- and O-dono ligands we e p epa ed and chemically, spec oscopically and c ys allog aphically s udied. In he inal phase, a magne ic s udy o selec ed complexes was ca ied ou . Conside ing he aims and all he achie ed esul s o he p esen hesis, i can be concluded: 1. Theo e ical aspec s o single-molecule magne ism we e desc ibed wi h espec o ansi ion me als and lan hanides. Special emphasis was placed on Ni(II) and Co(II)/Co(III) as 3d ansi ion me als and Ce(III), Gd(III) and Dy(III) among he lan hanides. The coo dina ion chemis y o selec ed ansi ion me als and lan hanides was in oduced, oo. The las pa o he heo e ical pa o he hesis is dedica ed o he cha ac e iza ion o he selec ed ligands and desc ip ion o he esul s o a li e a u e su ey o known complexes based on he selec ed ligands. 2. E o in he labo a o y wi h ull a en ion o de ails along wi h li e a u e sea ches led o he design o op imal syn he ic s a egies o he p epa a ion o he se ies o T (II)-Ln(III) he e odinuclea complexes. A sel -assembly s ep- wise app oach yielded se e al p ecu so s and inal p oduc s, which we e isola ed in c ys alline o m, pu i ied and cha ac e ized. The e we e 21 compounds p epa ed, 18 o hem a e me al complexes, 17 o hem a e newly p epa ed. Among hem, 9 we e he e onuclea . 3. X- ay single-c ys al s uc u e analysis was used o he c ys allog aphic s udy o 3 o ganic coumpounds and 18 complexes (3 based on Ni(II), 2 based on Co(II), 4 based on Co(III) and 9 Ni-Ln complexes). The esul s o s uc u e analysis ha e shown ha 8 complexes exhibi molecula mononuclea s uc u es, 9 molecula he e obime allic and 1 1D ionic s uc u e. Using s uc u e analysis, he phenomena o sol a omo phism, polymo phism, isomo phism and isos uc u ali y we e iden i ied. In addi ion, in he case o wo solids peculia empe a u e dependen s uc u al changes we e iden i ied and analysed in de ail. These p ocesses in he solid s a e made i possible o elucida e he c ys al s uc u es o complexes no accessible by solu ion me hods. This allowed us o 132 de e mine he c ys al s uc u e o compound/s which we e no easily p epa able by solu ion me hods. 4. 4 me al complexes we e chosen o magne ic s udies, h ee Ni-Ln bime allic compounds and one o cobal (II) benzoa e ihyd a e. All ou complexes displayed ield induced slow magne ic elaxa ion. Ou s anding indings came wi h ce ium(III) and gadolinium(III) samples as hese wo me al ions a e no conside ed as “ ypical” SMM ions as is dysp osium(III). Especially, a Ni-Gd complex wi h a diamagne ic Ni(II) ion and he usually magne ically iso opic Gd(III) ion b ough new insigh in o he heo y o single molecule magne ism. 5. The expe imen al esul s ob ained we e published in in e na ional scien i ic jou nals and p esen ed a se e al scien i ic con e ences as lec u es and pos e s. 139 7.3.3 P íp a a a cha ak e izácia he e onukleá nych zlúčenín Po úspešnej izolácii a cha ak e izácii p eku zo a [Ni(o- an-en)]·nH2O (4) sa pos upo alo podľa už u edenej s a égie. Najp sa ykonali expe imen y s dusičnanom gadolini ým ako lan anoido ou soľou. Syn éza sa usku očňo ala e anole p i podmienkach e luxu. Mik ok yš alický p oduk , k o ý sa izolo al il áciou bezp os edne po eakcii, sa ek yš alizo al z niekoľkých ozpúšťadiel alebo z ich zmesi (di úzne echniky k apalina-k apalina) s cieľom získať monok yš ály. Monok yš ály sa získali iba ek yš alizáciou z ace oni ilu, čím sa získal požado aný 3d-4 bime alický komplex [Ni(o- an-en)Gd(NO3)3]·2CH3CN (12), k o om a ómy Ni(II) a Gd(III) sú p emos ené d oma O-monoa ómo ými mos íkmi a a óm Gd(III) si dopĺňa koo dinačnú s é u (k.č. = 10) omi chelá o ými ni á o ligandmi. K yš ály 12 po izolácii z ma ečného lúhu sú nes abilné dôsledku desol a ácie. V ďalších expe imen och pomocou už u edenej „sel -assembly“ me ódy sa kombinácii s p eku zo om [Ni(o- an-en)]·nH2O (4) použili mies o dusičnano chlo idy lan anoido . Syn ézy sa usku očňo ali p i podmienkach e luxu, p ičom sa izolo ali o anžo é mik ok yš alické p áško é p oduk y šeobecného zloženia [Ni(o- an-en)LnCl3(H2O)], p ičom Ln p eds a uje Ce (13), Gd (14) a Dy (15). Iden i a a čis o a mik ok yš alických zo iek bola po dená pomocou IČ spek oskopie, elemen á nej analýzy a p áško ej g. di akčnej analýzy. Využi ím ôznych ek yš alizačných echník boli zlúčeniny 13, 14 a 15 p ip a ené aj podobe monok yš álo . Výsledky š uk ú nej analýzy ukázali, že še ky i komplexy sú na zájom izomo né; k yš alizujú monoklinickej g upe P21/n. Ich molekulo á š uk ú a pozos á a z neu álnej bime alickej d ojjad o ej komplexnej molekuly [Ni(o- an-en)LnCl3(H2O)], k o ej cen álny a óm Ni(II) je š o co o-planá ne koo dino aný dono o ým se om {N2O2} pochádzajúcim z ligandu Schi o ej bázy (o- an-en)2- (Ob . 7.3.1). Koo dináciu cen álneho a ómu lan anoidu o ia 4 a ómy kyslíka z ligandu (o- an-en)2-, jeden a óm kyslíka ak a ligandu a i chlo ido ligandy. K yš álo á š uk ú a zlúčenín 13, 14 a 15 je podpo ená s edne silnými odíko ými äzbami ypu O-HCl, čím sa y á a sup amolekulo á eťazo á š uk ú a pozdĺž osi a. Ďalšie slabšie odíko é äzby ypu Ca –HCl a Cimine–HCl a π-π in e akcie medzi a oma ickými jad ami susedných e iazok y á ajú sup amolekulo é s y ab o ine. Medzi sup amolekulo ými o inami sa našli len slabšie medzimolekulo é 140 kon ak y ypu C-HCl pochádzajúce z me ylo ých a me yléno ých skupín ligandu (o- an-en)2-. Ob ázok 7.3.1 Molekulo á š uk ú a komplexu 13. Teplo né elipsoidy (ok em a ómo odíka) sú yob azené s 50 % ú o ňou p a depodobnos i. Rek yš alizáciou d ojjad o ých komplexo [Ni(o- an-en)LnCl3(H2O)] (Ln = Ce, Dy) sa ep oduko a eľne izolo ali ďalšie komplexy: [Ni2Ce2(o- an-en)2Cl6] (16), [Ni(o- an-en)DyCl3] (17) a [Ni(o- an-en)DyCl3]·E OH (18). Tie o boli cha ake izo ané ob yklými me ódami a ich k yš álo é š uk ú y ( iď nižšie) boli s ano ené me ódou š uk ú nej analýzy. V ámci našich expe imen o s ek yš alizáciou p áško ej zo ky [Ni(o- an-en)CeCl3(H2O)] (13) sme usku očnili ek yš alizáciu z e anolu uza e ej nádobe umies nenej peci nas a enej na 80 °C. Monok yš álo á š uk ú na analýza y o ených če enoo anžo ých k yš álo ukázala, že ide o no ý š o jad o ý komplex [Ni2Ce2(o- an-en)2Cl6] (16). Jeho znik sa dá ys e liť dime izáciou d och š uk ú nych jedno iek [Ni(o- an-en)CeCl3(H2O)] dôsledku u oľnenia ak a ligando a následným y o ením d och chlo ido mos íko medzi a ómami Ce(III) zniklo jad o {CeCl2Ce}), čím sa koo dinačné číslo 8 a ómu Ce(III) zacho á a. Ro naký ek yš alizačný pos up sa apliko al aj na p áško ej zo ke komplexu [Ni(o- an-en)DyCl3(H2O)] (15). Nap iek p edpokladanej analógii medzi a ómami cé u a dysp ózia sa om o p ípade dime izácia nepozo o ala, ale po dehyd a ácii sa y o il d ojjad o ý dehyd a o aný komplex [Ni(o- an-en)DyCl3] (17). P edpokladáme, že Dy(III) s menšími ióno ým polome om ako Ce(III) [Shannon, 1976] ykazuje yššiu s abili u s ojej koo dinačnej s é y aj s nižším koo dinačným číslom 7, a p e o komplex 17 nemá endenciu dime izo ať. Pozo o aná dime izácia zlúčenine Ce(III) môže byť 141 eda dôsledkom snahy äčšieho a ómu Ce(III) zacho ať si koo dinačné číslo 8 koo dináciou mos íko ých chlo ido ligando . Také o sp á anie zá islos i od ióno ých polome o už bolo minulos i pozo o ané [Kano a kol., 2003; Baisch a kol., 2004; Deacon a kol., 2002; Wong a kol., 2006; Chen a kol., 2011]. Následne sme usku očnili expe imen y ek yš alizácií pomocou di úznych echník. Di úzia e anolo ého oz oku [Ni(o- an-en)DyCl3(H2O)] (15) do izop opanolu p i labo a ó nej eplo e posky la k yš ály [Ni(o- an-en)DyCl3]·E OH (18). Molekulo á š uk ú a komplexu 18 obsahuje neu álnu bime alickú komplexnú jedno ku [Ni(o- an- en)DyCl3], k o ej cen álny a óm Ni(II) leží o nú o nej du ine ligandu Schi o ej bázy s dono o ým se om {N2O2} a cen álny a óm Dy(III) obsadzuje onkajšiu du inu {O4}. Jeho koo dinačný polyéde je doplnený omi chlo ido ligandami. Ten o ýsledok podpo uje náš p edchádzajúci p edpoklad o s abili e cen álneho a ómu Dy(III) s koo dinačným číslom 7. P i zmene podmienok ek yš alizácie bola lá ka [Ni(o- an-en)DyCl3(H2O)] (15) ozpus ená zmesi e anol/izop opanol. K yš alizáciou z oh o oz oku p i z ýšenej eplo e (50 °C) sme získali če enoo anžo é p izma ické k yš ály s e eoizomé u pô odného komplexu, konk é ne o mu II komplexu [Ni(o- an-en)DyCl3(H2O)] (19). Š údium jeho k yš álo ej š uk ú y ukázalo, že komplexe 19 ( o ma II) op o i komplexu 15 ( o ma I) sú chlo ido ligandy umies nené koo dinačnom polyéd i Dy(III) odlišným spôsobom; kým 15 sú i chlo ido ligandy umies nené na jednej ploche polyéd a, 19 sú i chlo ido ligandy umies nené jednej o ine ezu polyéd a (Ob . 7.3.2a). Dôsledkom je, že 19 znikajú pomocu odíko ých äzieb ypu O-HCl sup amolekulo é dimé y. Dime izáciu [Ni(o- an-en)DyCl3(H2O)] (19) za zniku š o jad o ého komplexu [Ni2Dy2(o- an-en)2Cl6] (20) sa poda ilo dosiahnuť eakciou dehyd a ácie uhej áze. P iebeh dehyd a ácie sa š udo al na monok yš ále 19. Po jeho oh e e na eplo u asi 84 °C p ebehla dehyd a ácia a kedže sa p i om zacho al monok yš álo ý cha ak e zo ky, bolo možné s ano iť k yš álo ú š uk ú u 20. Tá o je o ená d oma š uk ú nymi jedno kami [NiDy(o- an-en)Cl3] p epojenými d oma mos íko ými chlo ido ligandmi (Ob . 7.3.2b). U edený p oces dehyd a ácie p eds a uje opo ak ickú eakciu ypu SC-SC (Single C ys al- o-Single C ys al). 142 a) b) Ob ázok 7.3.2 a) Po o nanie izomé o 15 ( ľa o) a 19 ( p a o). b) Zmena molekulo ej š uk ú y počas opo ak ickej dehyd a ácie: 2 19 → 20 + 2 H2O. 7.3.4 Magne ické las nos i sé ie he e onuklá nych komplexo [Ni(o- an-en)LnCl3(H2O)] [Ln = Ce (13), Gd (14), Dy (15)] Na š údium magne ických las nos í boli yb ané d ojjad o é Ni-Ln bime alické zlúčeniny 13, 14, 15 a zlúčenina Co(II) 21. Fázo á čis o a š udo aných zo iek bola po dená ön geno ou p áško ou di akčnou analýzou. Výsledky p áško ých di akčných me aní boli po o nané s di akčnými údajmi ypočí anými z ýsledko monok yš álo ej š uk ú nej analýzy 13-15 ykonanej p i izbo ej eplo e, p ičom sa použila LeBailo a me óda p og ame Jana2006 [Le Bail a kol., 1988; Le Bail, 2005; Pe říček a kol., 2014]. Magne ické me ania sa ykonali ok em DC ežimu aj AC ežime s cieľom o e iť p ípadné SMM cho anie š udo aných lá ok. Samo né expe imen y a yhodno enie boli ealizo ané p aco nou skupinou p o . Boču z Uni e zi y s . Cy ila a Me oda T na e. Z ýsledko š uk ú nej analýzy Ni-Ln d ojjad o ých komplexo 13, 14 a 15 ( iď yššie) yplý a, že a óm Ni(II) ých o komplexoch je koo dino aný š o co o, eda je diamagne ický. Dôsledkom u edeného je, že magne ické las nos i komplexo 13, 14 a 15 sú u čené p í omnými a ómami Ln, k o é ykazujú o bi álo ý aj spino ý momen hybnos i. Ich základné s a y sú mul iple y 2F5/2 p e Ce(III), 8S7/2 p e - 2 H2O 143 Gd(III) a 6H15/2 p ípade Dy(III), a ich p íslušné hodno y gJ sú 6/7, 2 a 4/3. Magne izácie p epoč e na zo co ú jedno ku sa majú sa u o ať p i hodno ách M1 = Mmol/(NAμB) = gJ·J = 6/7 × 5/2 = 15/7, 2 × 7/2 = 7 a 4/3 × 15/2 = 10 p e Ce(III), Gd(III) a Dy(III). E ek í ny magne ický momen , μe /μB = gJ[J(J + 1)]1/2, p e jedno li é komplexy dosahuje limi né hodno y 2,54 μB, 7,94 μB, a 10,6 μB. Expe imen álne zis ené e ek í ne magne ické momen y jedno li ých komplexo 13, 14 a 15 p i labo a ó nej eplo e ykazujú hodno y μe = 2,36 μB (Ce), 7,9 μB (Gd) a 12,15 μB (Dy), p ičom očaká ané hodno y sú 2,54 (Ce), 7,94 (Gd) a 10,6 μB (Dy). Vyššiu pozo o anú hodno u p e 15 (Dy) je možné ys e liť p í omnosťou nízko ležiacich exci o aných s a o susedného a ómu Ni(II). Exis enciu p íspe ku eplo ne nezá islého pa amagne izmu (TIP) dôsledku p í omného a ómu Ni(II) po dzuje aj mie ne lineá na eplo ná zá islosť μe p ípade komplexu 13. Expe imen álne hodno y sa u ácie magne izácie p i T = 2,0 K a B = 7 T p e jedno li é komplexy sú M1 = 1,0 (Ce), 6,6 (Gd) a 7,9 (Dy), p ičom ypočí ané hodno y p e izolo ané ióny sú 2,1 (Ce), 7,0 (Gd) a 10,0 (Dy). Nižšia pozo o aná hodno a p ípade komplexu Ce(III) naznačuje, že dôsledku pôsobenia k yš álo ého poľa je obsadený iba najnižší z och K ame o ých duble o . Na d uhej s ane, ý azne nižšia pozo o aná hodno a magne izácie p ípade komplexu Dy(III) naznačuje zníženie o bi álo ého p íspe ku buď dôsledku asyme ie koo dinačnej s é y a ómu Dy(III) a / alebo ply u š iepenia základného mul iple u k yš álo ého poľa nulo om poli. Údaje o AC suscep ibili e sa získali p i ampli úde poľa BAC = 0,38 mT a me ali sa zá islos i od onkajšieho magne ického poľa BDC, eplo y T a ek encie oscilujúceho poľa. AC magne ické me ania še kých och komplexo á ane nominálne izo opného sys ému na báze Gd(III) (14) ukázali, že še ky i komplexy 13, 14 a 15 ykazujú poľom induko anú pomalú magne ickú elaxáciu s d oma alebo omi elaxačnými kanálmi. V p ípade komplexu 13 (Ce) ek enčná zá islosť mimo ázo ej zložky suscep ibili y χ″ poukazuje p i eplo ách pod 4 K na exis enciu d och elaxačných kanálo s dominan ným p íspe kom nízko ek enčnej zložky, p ičom nad ou o eplo ou p íspe ok HF zložky ymizne. Relaxačný čas p i T = 1,9 K a BDC = 0,5 T má hodno u τ(LF) = 60,3 ms, k o ý je dlhší po o naní s hodno ou τ(LF) = 18,7 ms p i BDC = 0,1 T. 144 Exis encia pomalej magne ickej elaxácie p ípade izo opného a ómu Gd(III) bola p ek apujúca. F ek enčná zá islosť oboch zložiek AC suscep ibili y p e zlúčeninu 14 odhalila exis enciu d och elaxačných kanálo , p ičom sa zis ilo, že eplo nom in e ale 1,9 až 6,5 K je elaxačný čas HF kanála eplo ne iba mie ne zá islý. Ok em oho ysoko ek enčný kanál HF ykazuje „z láš ne“ sp á anie: p i ochladení elaxačný čas p echádza maximom a následne sa sk acuje: τ(HF) = 223 μs p i T = 3,9 K po o naní s τ(HF) = 120 μs p i T = 1,9 K. Relaxačný čas p e LF p oces p i BDC = 0.3 T a T = 1,9 K je τ(LF) = 0,37 s. Analýzou ek enčnej zá islos i ázo ej a mimo ázo ej čas i AC suscep ibili y zo ky 15 (Dy) sa zis ila exis encia och elaxačných kanálo : nízko ek enčného (LF), s edo ek enčného (IF) a ysoko ek enčného (HF). Kým p i najnižšej me anej eplo e T = 1,9 K dominuje nízko ek enčná zložka, jej p íspe ok s as úcou eplo ou klesá p ospech ysoko ek enčnej zložky. P i najnižšej me acej eplo e, T = 1,9 K a p i BDC = 0.15 T sa iden i iko ali i elaxačné časy τ(LF) = 1,29 s, τ(IF) = 74 ms a τ(HF) = 964 μs. Z ho eu edeného yplý a, že še ky i š udo ané zlúčeniny, á ane Gd(III) (14), ykazujú pomalú magne ickú elaxáciu. Vo še kých och zlúčeninách sú še ky i chlo ido ligandy umies nené na jednej ploche koo dinačného polyéd a. Ten o spôsob umies nenia p ipomína ac-kon igu áciu a znamená, že sú koncen o ané ej is ej čas i koo dinačnej s é y, za iaľ čo iné š udo ané analogické komplexy ykazujú syme ickejšiu dis ibúciu chlo ido ligando . Usudzujeme, že á o kon igu ácia o ply ňuje dis ibúciu elek óno na cen álnom a óme ( náša anizo opiu do dis ibúcie) a podpo uje SMM sp á anie ých o komplexo , a o z iedka o aj p e komplex Gd(III). Ukázalo sa, že geome ia a hus o a elek óno koo dinačných mies majú eľmi dôleži ý ply na SMM sp á anie lan anoido ých ióno . Výskum magne izmu komplexo Co(II) posledných časoch ukázal, že ie o sys émy majú eľmi ysokú magne ickú anizo opiu, k o á as ie po adí e a-, pen a- a hexakoo dinácie komplexo [C aig & Mu ie, 2015; Gomez-Coca a kol., 2015; F os a kol., 2016]. Z u edeného dô odu sa na š údium magne ických las nos í yb al aj komplex 21 obsahujúci cen álny a óm Co(II), p ičom a ómy Co(II) sú na yše uspo iadané do eťazca. Me ania DC poli ukázali, že e ek í ny magne ický momen μe lá ky 21 sa p i poklese eplo y z yšuje z hodno y μe = 5,6 μB na maximum μe = 15,9 μB p i T = 6,5 145 K a následne po om ýchlo klesne na hodno u μe = 8,0 μB p i T = 1,9 K. Tie o údaje naznačujú p echod pa amagne ickej ázy s ýmennými in e akciami e omagne ickej po ahy na an i e omagne ickú ázu p i eplo e TN = 5,5 K. F ek enčná zá islosť oboch zložiek suscep ibili y AC poli poukázala na exis enciu d och maxím k i ke χ″ op o i , k o á naznačuje p í omnosť d och elaxačných kanálo . Nás up nízko ek enčného (LF) módu je dob e idi eľný ozsahu T = 1,9 - 3,3 K. Nad 3,9 K je mimo ázo á suscep ibili a po lačená a po om sa zo ka s á a pa amagne om. LF pás začína ásť pod 1 Hz a jeho maximum leží mimo limí me ania – 0,1 Hz. Relaxačný čas ak dosahuje hodno u τ(LF) > 1,6 s p i nízkych eplo ách bez ohľadu na spôsob i o ania ( o znamená, že τLF (2,1 K) = 14 s). Mimo ázo á zložka suscep ibili y p e BDC = 0,1 T s úpa na maximum p i T = 4,1 K a po om sa p i ďalšom zah ie aní ýchlo zoslabuje. P i TN > 4,7 K je akme nulo á k ôli pa amagne ickej áze. 7.4 Zá e Výsledky p edkladanej dize ačnej p áce s ohľadom na jej s ano ené ciele je možné zh núť nasledo aných bodoch: 1. Bola opísaná eó ia jednomolekulo ého magne izmu s ohľadom na p echodné ko y a lan anoidy. Osobi ný dô az sa kládol na magne ické las nos i yb aných 3d p ko Ni(II) a Co(II) / Co(III) a yb aných 4 p ko Ce(III), Gd(III) a Dy(III). Na základe pozna ko získaných las nou eše šou pô odnej li e a ú e a da abázach bola disku o aná aj koo dinačná chémia u edených yb aných 3d a 4 cen álnych a ómo , ako aj použi ých ypo ligando . 2. Na základe údajo li e á nej eše še a expe imen álnych skúsenos í sa yp aco al ná h s a égie syn éz he e odinukleá nych komplexo T (II)- Ln(III). Ten o z . „sel -assembly“ syn e ický pos up je ojk oko ý a jeho použi ie iedlo k izolácií iace ých zlúčenín, k o é boli izolo ané, p ípade po eby p ečis ené ek yš alizáciou a následne cha ak e izo ané chemickými, spek oskopickými a ďalšími me ódami. Bolo p ip a ených 21 zlúčenín, z k o ých 18 sú komplexné zlúčeniny (17 no ých) a 3 o ganické lá ky. Spomedzi 18 komplexných zlúčenín bolo 9 3d-4 he e onukleá nych. Osobi ný dô az sa kládol na p íp a u monok yš álo , p e o na ich p íp a u sa použili ôzne di úzne echniky. 146 3. Pomocou me ódy š uk ú nej analýzy sa š udo ala k yš álo á š uk ú a 3 o ganických zlúčenín, 3 zlúčenín Ni(II), 2 zlúčenín Co(II), 4 Co(III), ako aj 9 Ni-Ln komplexo . Výsledky š uk ú nej analýzy ukázali, že 8 komplexo malo molekulo ú jednojad o ú š uk ú u, 9 molekulo ú he e obime alickú a jedna zlúčenina ykazo ala ióno ú 1D š uk ú u. Pomocou ýsledko ej o me ódy sa iden i iko ali d ojice, esp. ojice komplexo , k o é ykazo ali sol a omo izmus a polymo iu, esp. boli izoš uk ú ne. V p ípade d och {Ni- Ln} d ojjad o ých komplexo sa pozo o ali a pod obne analyzo ali eplo ne zá islé š uk ú ne zmeny, p i k o ých sa zacho á al monok yš álo ý cha ak e zo ky; o umožnilo s ano enie k yš álo ej š uk ú y lá ky, k o ú nebolo možné p ip a iť oz oko ými me ódami. 4. Š udo ali sa magne ické las nos i š y och yb aných komplexo , ihyd á u benzoanu kobal na ého s 1D š uk ú ou a och Ni-Ln d ojjad o ých molekulo ých komplexo . Vše ky š udo ané lá ky ykazo ali pomalú magne ickú elaxáciu a eda pa ia do ka egó ie SMM. Ako naj ýznamnejší ýsledok ej o oblas i je možné po ažo ať SMM cha ak e Ni-Gd komplexu obsahujúceho nominálne izo opný ión Gd(III) p í omnos i diamagne ického a ómu Ni(II). 5. Získané expe imen álne ýsledky boli publiko ané o edeckých časopisoch a p ezen o ané na ôznych edeckých poduja iach o mo pos e o a p ednášok. 147 8 Resumen en español 8.1 In oducción En las úl imas es décadas, se han es udiado me ales de ansición de p ime a ila como Mn(III), Fe(III), Fe(II), Co(II) y Ni(II) desde el pun o de is a del magne ismo molecula . Sin luga a dudas, la a ención más in ensa se p es a a los llamados "single- molecule magne s" (SMMs) que son especies molecula es que mues an a ias p opiedades magné icas ca ac e ís icas, como la unelización de la magne ización y la elajación len a de la magne ización. El aspec o undamen al de los SMMs es que pueden magne iza se median e un campo magné ico ex e no y, una ez que se elimina el campo, pueden p ese a es a magne ización du an e un iempo de e minado (a una empe a u a de e minada). Es a his é esis magné ica se llama elajación len a de la magne ización. Como es a elajación iene un o igen pu amen e molecula , el ma e ial se llama "single-molecule magne ". Es os ma e iales se pueden u iliza en disposi i os elec ónicos de almacenamien o de in o mación de al a densidad basados en espines. Esquema 8.1.1 Diag ama de "doble pozo" que mues a el p oceso de magne ización y elajación en SMM. La elajación len a de la magne ización se puede desc ibi median e el simple diag ama de "doble pozo" (Esquema 8.1.1.). Todos los ni eles de ene gía MS es án localizados en dos pozos iguales, –MS en la izquie da, + MS en la de echa. Cuando no se aplica un campo ex e no, odos los ni eles de ene gía de ± MS son pa es degene ados (excep o MS = 0) y los pozos es án igualmen e poblados. En el campo magné ico 148 ex e no pa alelo al eje de magne ización, los ni eles de –MS se es abilizan en pe juicio de los de + MS (no a: el campo aplicado es pa alelo al eje z, los ni eles de + MS co esponden a una p oyección de la magne ización an ipa alela al campo y – MS ni eles co esponden a la magne ización pa alela al campo ex e no aplicado). Cuando se elimina un campo ex e no, el sis ema uel e al equilib io é mico. El amaño de la ba e a de ene gía e ec i a (Ue ) se e a ec ado po dos pa áme os, a sabe , el es ado de espín básico (S) y el pa áme o de aniso opía magné ica (D). Po el en oque simple, cuan o mayo sea la ba e a de ene gía Ue en e los ni eles de espín in e sos, mayo se á el iempo de elajación obse ado. En gene al, un es ado undamen al de al o espín combinado con una ue e aniso opía magné ica es la ca ac e ís ica eque ida pa a los SMMs [Neese & Pan azis, 2011]. Esos dos pa áme os que a ec an el amaño de la ba e a de ene gía e ec i a (Ue ) pa a los SMM basados en me ales de ansición, son in e samen e p opo cionales en e sí, lo que e i a un mejo a signi ica i a en las p opiedades SMM [Ahmed e al., 2014]. Con espec o a eso, se ha usado una combinación de lan ánidos e iones de me ales de ansición en un es ue zo po aumen a la aniso opía magné ica máxima. Un es udio ecien e sob e los complejos 3d-4 con iones me álicos 3d diamagné icos como el zinc(II) o el cobal o(III) mos ó la mejo a de la ba e a Ue en compa ación con sus análogos de lan ánidos mononuclea es [Fondo e al., 2017]; se sugi ió que la p esencia de un ca ión 3d diamagné ico ce ca del á omo cen al de lan ánido, ambos compa iendo un á omo de puen e de oxígeno, induce una g an pola ización de ca ga en el á omo de oxígeno de puen e que a o ece un aumen o en la ba e a Ue . Es a obse ación in oca una nue a es a egia en el diseño de los complejos 3d-4 con iones diamagné icos 3d [Langley e al., 2012; Langley e al., 2013; Upadhyay e al., 2014; Sun e al., 2016; Upadhyay e al., 2017]. El c ecien e in e és en los complejos he e ome álicos en a ios campos ha inspi ado el diseño de ligandos capaces de coo dina un núme o solici ado y un ipo de cen o de me al. El au oensamblaje sin e iza el manejo de p ecu so es, ya que los bloques de cons ucción son una ins alación ú il pa a ob ene p oduc os deseables, especialmen e cuando que emos log a un complejo con p opiedades ísicas o químicas especiales. El con ol sob e la ca ga, la nuclea idad o la dimensionalidad de los p oduc os inales puede se el ac o c í ico en el éxi o de una sín esis di igida.