Extended BODIPYs as Red–NIR Laser Radiation Sources with Emission from 610 nm to 750 nm

Ci a ion: Oliden-Sánchez, A.; Al a ado-Ma ínez, E.; Ramí ez-O nelas, D.E.; Vázquez, M.A.; A ellanal-Zaballa, E.; Bañuelos, J.; Peña-Cab e a, E. Ex ended BODIPYs as Red–NIR Lase Radia ion Sou ces wi h Emission om 610 nm o 750 nm. Molecules 2023,28, 4750. h ps://doi.o g/ 10.3390/molecules28124750 Academic Edi o : Lucia Panzella Recei ed: 18 May 2023 Re ised: 11 June 2023 Accep ed: 12 June 2023 Published: 13 June 2023 Copy igh : © 2023 by he au ho s. Licensee MDPI, Basel, Swi ze land. This a icle is an open access a icle dis ibu ed unde he e ms and condi ions o he C ea i e Commons A ibu ion (CC BY) license (h ps:// c ea i ecommons.o g/licenses/by/ 4.0/). molecules A icle Ex ended BODIPYs as Red–NIR Lase Radia ion Sou ces wi h Emission om 610 nm o 750 nm Ainhoa Oliden-Sánchez 1, En ique Al a ado-Ma ínez 2, Diana E. Ramí ez-O nelas 2, Miguel A. Vázquez 2, Edu ne A ellanal-Zaballa 1, Jo ge Bañuelos 1,* and Edua do Peña-Cab e a 2,* 1 Depa amen o de Química Física, Uni e sidad del País Vasco (UPV/EHU), Ba io Sa iena s/n, Ap ado 644, 48940 Leioa, Bizkaia, Spain; [email p o ec ed] (A.O.-S.); [email p o ec ed] (E.A.-Z.) 2Depa amen o de Química, Uni e sidad de Guanajua o, No ia Al a s/n, Guanajua o 36050, Guanajua o, Mexico; [email p o ec ed] (E.A.-M.); [email p o ec ed] (D.E.R.-O.); [email p o ec ed] (M.A.V.) *Co espondence: [email p o ec ed] (J.B.); edua [email p o ec ed] (E.P.-C.) Abs ac : He ein, we epo he syn he ic access o a se o π -ex ended BODIPYs ea u ing a pen a- a yla ed (phenyl and/o hiophene) dipy in amewo k. We ake ad an age o he ull chemose- lec i e con ol o 8-me hyl hio-2,3,5,6- e ab omoBODIPY when we conduc he Liebeskind–S ogl c oss-coupling (LSCC) o unc ionalize exclusi ely he meso-posi ion, ollowed by he e a-Suzuki eac ion o a yla e he halogena ed si es. All hese lase dyes display abso p ion and emission bands in he ed edge o he isible spec um eaching he nea -in a ed wi h hiophene unc ionaliza ion. The emission e iciency, bo h luo escence and lase , o he polyphenylBODIPYs can be enhanced upon deco a ion o he pe iphe al phenyls wi h elec on dono /accep o g oups a pa a posi ions. Al e na i ely, he poly hiopheneBODIPYs show an as onishing lase pe o mance despi e he cha ge ans e cha ac e o he emi ing s a e. The e o e, hese BODIPYs a e sui able as a pale e o s able and b igh lase sou ces co e ing he spec al egion om 610 nm o 750 nm. Keywo ds: BODIPY; cha ge ans e ; dyes/pigmen s; luo escence; lase spec oscopy 1. In oduc ion The ques o no el a - ed and nea -in a ed (NIR) luo opho es is an eme ging ield in dye chemis y [ 1 – 3 ]. Nowadays, luo escen imaging has become a powe ul ool o isualize biological sys ems and ack biomolecules unde ad anced luo escen mic o- scopes wi h supe esolu ion (single molecule) [ 4 – 6 ]. This echnique demands molecula p obes wo king in he so-called biological o he apeu ic window (beyond 650 nm), owing o he deep- issue pene a ion o his long-wa eleng h adia ion (2–5 cm) [ 7 – 10 ]. These luo opho es should be chemically obus and pho os able in o de o display long las ing luo escen images, and eadily a ailable o pos - unc ionaliza ion o allow a ge able la- belling [ 11 ]. Ano he aspec o hese ed–NIR luminopho es is he de elopmen o low-cos exci a ion sou ces in op ical ibe s applied in elecommunica ions ( elecom ange beyond 800 nm) owing o he lowe in e e ence and sca e ing o his long-wa eleng h adia ion wi h i s su oundings, allowing he ligh o a el longe dis ances [12,13]. Among he a ious classes o o ganic dyes es ed as ligh emission sou ces in his sough a e spec al window (mainly based on cyanine, po phy in and ph alocyanine skele- ons) [ 14 , 15 ], BODIPY de i a i es a e in he spo ligh [ 16 , 17 ]. This mode n luo opho e, a s uc u al analogue o po phy in, enables applica ion o se e al syn he ic s a egies o push he abso p ion and emission owa ds longe wa eleng hs while e aining hei excellen pho ophysical signa u es [ 18 – 20 ]. Acco ding o he li e a u e, se e al app oaches ha e been success ully es ed o span he delocalized π -sys em o he dipy in co e and each he ed–NIR spec al window. The main s a egies in ol e he usion o a oma ic ings (a yls and he e ocycles, and e en o he BODIPYs) [ 21 – 23 ], pe iphe al linkage o a oma ic Molecules 2023,28, 4750. h ps://doi.o g/10.3390/molecules28124750 h ps://www.mdpi.com/jou nal/molecules Molecules 2023,28, 4750 2 o 15 amewo ks ( o ins ance, s y yls and he a o emen ioned cyclic moie ies) [ 24 – 26 ], eplace- men o he meso-ca bon by ni ogen (aza-BODIPYs) [ 27 , 28 ], g a ing elec on eleasing and wi hd awing unc ionaliza ions (push-pull BODIPYs) [ 29 , 30 ], and he combina ion o some o hese molecula s a egies in o a single s uc u e [ 31 ]. F om such su eys, we ind ha he e he ing o a oma ic amewo ks, p ope ly unc ionalized wi h elec on ich g oups, a he py olic β and α posi ions, is one o he success ul s a egies o induce p onounced spec al shi s, while e aining he high abso p ion and emission e iciency cha ac e is ics o his amily o dyes. Mo eo e , i would be highly ad an ageous o ha e ull con ol o he unc ionaliza ion o he di e en BODIPY posi ions o be able o ailo he physical (e.g., solubili y) and pho ophysical p ope ies o he inal p oduc s. In espec o his backg ound, we syn hesized wo se s o 8-a ylBODIPY-based lu- o opho es (Scheme 1). On he one hand, we syn hesized polya yla ed BODIPYs bea ing 2,3,5,6-phenyls pa a- unc ionalized wi h elec on wi hd awing ( o myl, i luo ome hyl and cyano) and elec on neu al o dono g oups ( ime hylsilyl and me hoxy). On he o he hand, we syn hesized poly hiopheneBODIPYs bea ing such sul u -con aining he e- ocycles a he same abo e-men ioned posi ions. To asce ain he ole o he 8-a yl g oup, i s s e eoelec onic p ope ies we e sys ema ically a ied, adding s e ic cons ain s ia o ho-me hyla ion o g a ing elec on dono (me hoxy) o accep o ( o myl) g oups a i s pa a posi ion. The main aim o hese long-wa eleng h emi ing π -ex ended BODIPYs is o deciphe he s uc u al ac o s ha igge he spec al shi and he emission e iciency (bo h luo escence and lase ) and p o ide a cha o luo opho es ha a e e icien and s able a - ed–NIR lase sou ces. Acco dingly, we ha e e alua ed hei pho onic signa u es unde so (pho ophysical p ope ies) and ha d (lase pe o mance) i adia ion egimes and a ionalized hem assis ed by compu a ional simula ions. Molecules 2023, 28, x FOR PEER REVIEW 2 o 15 se e al app oaches ha e been success ully es ed o span he delocalized π-sys em o he dipy in co e and each he ed–NIR spec al window. The main s a egies in ol e he usion o a oma ic ings (a yls and he e ocycles, and e en o he BODIPYs) [21–23], pe iphe al linkage o a oma ic amewo ks ( o ins ance, s y yls and he a o emen ioned cyclic moie ies) [24–26], eplacemen o he meso-ca bon by ni ogen (aza-BODIPYs) [27,28], g a ing elec on eleasing and wi hd awing unc ionaliza ions (push-pull BODIPYs) [29,30], and he combina ion o some o hese molecula s a egies in o a single s uc u e [31]. F om such su eys, we ind ha he e he ing o a oma ic amewo ks, p ope ly unc ionalized wi h elec on ich g oups, a he py olic β and α posi ions, is one o he success ul s a egies o induce p onounced spec al shi s, while e aining he high abso p ion and emission e iciency cha ac e is ics o his amily o dyes. Mo eo e , i would be highly ad an ageous o ha e ull con ol o he unc ionaliza ion o he di e en BODIPY posi ions o be able o ailo he physical (e.g., solubili y) and pho ophysical p ope ies o he inal p oduc s. In espec o his backg ound, we syn hesized wo se s o 8-a ylBODIPY-based luo opho es (Scheme 1). On he one hand, we syn hesized polya yla ed BODIPYs bea ing 2,3,5,6-phenyls pa a- unc ionalized wi h elec on wi hd awing ( o myl, i luo ome hyl and cyano) and elec on neu al o dono g oups ( ime hylsilyl and me hoxy). On he o he hand, we syn hesized poly hiopheneBODIPYs bea ing such sul u -con aining he e ocycles a he same abo e-men ioned posi ions. To asce ain he ole o he 8-a yl g oup, i s s e eoelec onic p ope ies we e sys ema ically a ied, adding s e ic cons ain s ia o ho-me hyla ion o g a ing elec on dono (me hoxy) o accep o ( o myl) g oups a i s pa a posi ion. The main aim o hese long-wa eleng h emi ing π-ex ended BODIPYs is o deciphe he s uc u al ac o s ha igge he spec al shi and he emission e iciency (bo h luo escence and lase ) and p o ide a cha o luo opho es ha a e e icien and s able a - ed–NIR lase sou ces. Acco dingly, we ha e e alua ed hei pho onic signa u es unde so (pho ophysical p ope ies) and ha d (lase pe o mance) i adia ion egimes and a ionalized hem assis ed by compu a ional simula ions. Scheme 1. Molecula s uc u e o he ed–NIR emi ing BODIPYs. 2. Resul s and Discussion 2.1. Syn hesis Recen ly, we epo ed he syn hesis o no el BODIPY building block 2 h ough a e ab omina ion eac ion o comme cially a ailable 8-me hyl hioBODIPY 1 and demons a ed ha i displayed o hogonal eac i i y [32]. The C–S bond was ac i a ed unde Liebeskind–S ogl c oss-coupling eac ion (LSCC) condi ions, lea ing he C–B bonds in ac [33]. This esul allowed he selec i e unc ionaliza ion o he meso-posi ion lea ing he o he b omina ed posi ions a ailable o be manipula ed a will. In his con ex , Scheme 1. Molecula s uc u e o he ed–NIR emi ing BODIPYs. 2. Resul s and Discussion 2.1. Syn hesis Recen ly, we epo ed he syn hesis o no el BODIPY building block 2 h ough a e ab omina ion eac ion o comme cially a ailable 8-me hyl hioBODIPY 1 and demon- s a ed ha i displayed o hogonal eac i i y [ 32 ]. The C–S bond was ac i a ed unde Liebeskind–S ogl c oss-coupling eac ion (LSCC) condi ions, lea ing he C–B bonds in- ac [ 33 ]. This esul allowed he selec i e unc ionaliza ion o he meso-posi ion lea ing he o he b omina ed posi ions a ailable o be manipula ed a will. In his con ex , we decided o e alua e a quad uple Suzuki–Miyau a c oss-coupling eac ion o ob ain a new amily o poly (he )a ylBODIPY dyes (Scheme 2). Molecules 2023,28, 4750 3 o 15 Molecules 2023, 28, x FOR PEER REVIEW 3 o 15 we decided o e alua e a quad uple Suzuki–Miyau a c oss-coupling eac ion o ob ain a new amily o poly (he )a ylBODIPY dyes (Scheme 2). Scheme 2. Re osyn he ic analysis o he syn hesis o poly-(he )a ylBODIPYs. We ini ially syn hesized BODIPY 2 acco ding o Scheme 3. Scheme 3. Syn hesis o he e ab omina ed 8-me hyl hioBODIPY p ecu so 2. Wi h 2 in hand, a chemoselec i e LSCC eac ion was ca ied ou o access e ab omina ed meso-a ylBODIPYs 3 acco ding o Scheme 4. Se e al a ylbo onic acids we e e alua ed, accessing i e de i a i es in modes o good yields (18–76%) in sho eac ion imes. Scheme 4. Syn hesis o e ab omina ed meso-a ylBODIPYs ia LSCC eac ion, s uc u e o he ed– NIR emi ing BODIPYs. Condi ions: BODIPY 2 (1 equi .), bo onic acid (3 equi .), Pd2(dba)3 (2.5 mol%), TFP (7.5 mol%), CuTC (3 equi .) in THF (0.03 M) a 55 °C. Scheme 2. Re osyn he ic analysis o he syn hesis o poly-(he )a ylBODIPYs. We ini ially syn hesized BODIPY 2acco ding o Scheme 3. Molecules 2023, 28, x FOR PEER REVIEW 3 o 15 we decided o e alua e a quad uple Suzuki–Miyau a c oss-coupling eac ion o ob ain a new amily o poly (he )a ylBODIPY dyes (Scheme 2). Scheme 2. Re osyn he ic analysis o he syn hesis o poly-(he )a ylBODIPYs. We ini ially syn hesized BODIPY 2 acco ding o Scheme 3. Scheme 3. Syn hesis o he e ab omina ed 8-me hyl hioBODIPY p ecu so 2. Wi h 2 in hand, a chemoselec i e LSCC eac ion was ca ied ou o access e ab omina ed meso-a ylBODIPYs 3 acco ding o Scheme 4. Se e al a ylbo onic acids we e e alua ed, accessing i e de i a i es in modes o good yields (18–76%) in sho eac ion imes. Scheme 4. Syn hesis o e ab omina ed meso-a ylBODIPYs ia LSCC eac ion, s uc u e o he ed– NIR emi ing BODIPYs. Condi ions: BODIPY 2 (1 equi .), bo onic acid (3 equi .), Pd2(dba)3 (2.5 mol%), TFP (7.5 mol%), CuTC (3 equi .) in THF (0.03 M) a 55 °C. Scheme 3. Syn hesis o he e ab omina ed 8-me hyl hioBODIPY p ecu so 2. Wi h 2 in hand, a chemoselec i e LSCC eac ion was ca ied ou o access e ab omi- na ed meso-a ylBODIPYs 3 acco ding o Scheme 4. Se e al a ylbo onic acids we e e alua ed, accessing i e de i a i es in modes o good yields (18–76%) in sho eac ion imes. Molecules 2023, 28, x FOR PEER REVIEW 3 o 15 we decided o e alua e a quad uple Suzuki–Miyau a c oss-coupling eac ion o ob ain a new amily o poly (he )a ylBODIPY dyes (Scheme 2). Scheme 2. Re osyn he ic analysis o he syn hesis o poly-(he )a ylBODIPYs. We ini ially syn hesized BODIPY 2 acco ding o Scheme 3. Scheme 3. Syn hesis o he e ab omina ed 8-me hyl hioBODIPY p ecu so 2. Wi h 2 in hand, a chemoselec i e LSCC eac ion was ca ied ou o access e ab omina ed meso-a ylBODIPYs 3 acco ding o Scheme 4. Se e al a ylbo onic acids we e e alua ed, accessing i e de i a i es in modes o good yields (18–76%) in sho eac ion imes. Scheme 4. Syn hesis o e ab omina ed meso-a ylBODIPYs ia LSCC eac ion, s uc u e o he ed– NIR emi ing BODIPYs. Condi ions: BODIPY 2 (1 equi .), bo onic acid (3 equi .), Pd2(dba)3 (2.5 mol%), TFP (7.5 mol%), CuTC (3 equi .) in THF (0.03 M) a 55 °C. Scheme 4. Syn hesis o e ab omina ed meso-a ylBODIPYs ia LSCC eac ion, s uc u e o he ed–NIR emi ing BODIPYs. Condi ions: BODIPY 2 (1 equi .), bo onic acid (3 equi .), Pd 2 (dba) 3 (2.5 mol%), TFP (7.5 mol%), CuTC (3 equi .) in THF (0.03 M) a 55 ◦C. Nex , he key s ep o ou syn he ic plan was conduc ed, ha is, he mul iple unc ion- aliza ion o he b omina ed posi ions ia he Suzuki–Miyau a c oss-coupling eac ion in 3a (Table S1). The eac ion condi ions used in en y 1 and 2 we e epo ed in he li e a u e o he mul iple unc ionaliza ion o BODIPYs [ 34 , 35 ]. Fo en y 1, he eac ion was incomple e, Molecules 2023,28, 4750 4 o 15 and mul iple p oduc s we e obse ed, while o en y 2, he desi ed p oduc 4 was isola ed in 42% yield. When we used Pd(OAc) 2 and SPhos, along wi h K 3 PO 4 as a base, he yield o 4 inc eased o 52% (en y 3 in Table S1). Once he bes condi ions we e de e mined, we se ou o eac 3a – e wi h se e al (he )a ylbo onic acids o di e en elec onic na u es o s udy he scope o he Suzuki–Miyau a c oss-coupling eac ion. The esul s ob ained o he mul iple unc ionaliza ion o 3a – e a e shown in Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ions ook place smoo hly and ga e he poly (he )a yla ed p oduc s in modes o good yields (41 o 83%) in ela i ely sho eac ion imes. In gene al, elec on- ich bo onic acids ga e he highes yields (en ies 1–4, 9 and 11 in Table 1) and sho es eac ion imes. Speci ically, he bes esul s, bo h in yield (65 o 83%) and eac ion imes, we e ob ained using 2- hienylbo onic acid, since he eac ions ook only 20 min. While he elec on-poo bo onic acids equi ed longe eac ion imes (en ies 10 and 12 in Table 1). No clea end was obse ed when he meso-a yl subs i uen s we e modi ied. Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ion on 3a–e1. Molecules 2023, 28, x FOR PEER REVIEW 4 o 15 Nex , he key s ep o ou syn he ic plan was conduc ed, ha is, he mul iple unc ionaliza ion o he b omina ed posi ions ia he Suzuki–Miyau a c oss-coupling eac ion in 3a (Table S1). The eac ion condi ions used in en y 1 and 2 we e epo ed in he li e a u e o he mul iple unc ionaliza ion o BODIPYs [34,35]. Fo en y 1, he eac ion was incomple e, and mul iple p oduc s we e obse ed, while o en y 2, he desi ed p oduc 4 was isola ed in 42% yield. When we used Pd(OAc)2 and SPhos, along wi h K3PO4 as a base, he yield o 4 inc eased o 52% (en y 3 in Table S1). Once he bes condi ions we e de e mined, we se ou o eac 3a–e wi h se e al (he )a ylbo onic acids o di e en elec onic na u es o s udy he scope o he Suzuki– Miyau a c oss-coupling eac ion. The esul s ob ained o he mul iple unc ionaliza ion o 3a–e a e shown in Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ions ook place smoo hly and ga e he poly (he )a yla ed p oduc s in modes o good yields (41 o 83%) in ela i ely sho eac ion imes. In gene al, elec on- ich bo onic acids ga e he highes yields (en ies 1–4, 9 and 11 in Table 1) and sho es eac ion imes. Speci ically, he bes esul s, bo h in yield (65 o 83%) and eac ion imes, we e ob ained using 2- hienylbo onic acid, since he eac ions ook only 20 min. While he elec on-poo bo onic acids equi ed longe eac ion imes (en ies 10 and 12 in Table 1). No clea end was obse ed when he meso-a yl subs i uen s we e modi ied. Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ion on 3a–e 1. En y A R-B(OH)2 Reac ion Time Yield 2 (%) Compound 1 S 20 min 80 4a 2 S 20 min 83 4b 3 S 20 min 65 4c 4 MeO S 25 min 76 4d 5 OHC S 2 h 55 4e 6 4 h 52 4 7 4 h 57 4g 8 F 3 C 5 h 41 4h 9 MeO 2 h 65 4i 10 MeOC 14 h 65 4j 11 MeO Me 3 Si 4 h 63 4k 12 MeO NC 16 h 57 4l 1 Condi ions: 3a (1 equi .), bo onic acid (8 equi .) Pd(OAc)2 (10 mol%), SPhos (22 mol%), K3PO4 (16 equi .) in PhCH3 a 90 °C oo no e. 2 Isola ed yield. 2.2. Pho ophysical P ope ies The a yla ion o he py oles ex ends he ch omopho ic delocalized π-sys em pushing he spec al bands owa ds he ed edge o he isible (abso p ion and emission o 4 and 4g placed a a ound 590 and 620 nm, espec i ely, Figu e 1). The meso-phenyl does no ake pa in he delocalized amewo k o he dipy in owing o i s wis ed geome ical a angemen ( heo e ically p edic ed o sion angle a ound 70° om g ound En y A R-B(OH)2Reac ion Time Yield 2 (%) Compound 1 Molecules 2023, 28, x FOR PEER REVIEW 4 o 15 Nex , he key s ep o ou syn he ic plan was conduc ed, ha is, he mul iple unc ionaliza ion o he b omina ed posi ions ia he Suzuki–Miyau a c oss-coupling eac ion in 3a (Table S1). The eac ion condi ions used in en y 1 and 2 we e epo ed in he li e a u e o he mul iple unc ionaliza ion o BODIPYs [34,35]. Fo en y 1, he eac ion was incomple e, and mul iple p oduc s we e obse ed, while o en y 2, he desi ed p oduc 4 was isola ed in 42% yield. When we used Pd(OAc)2 and SPhos, along wi h K3PO4 as a base, he yield o 4 inc eased o 52% (en y 3 in Table S1). Once he bes condi ions we e de e mined, we se ou o eac 3a–e wi h se e al (he )a ylbo onic acids o di e en elec onic na u es o s udy he scope o he Suzuki– Miyau a c oss-coupling eac ion. The esul s ob ained o he mul iple unc ionaliza ion o 3a–e a e shown in Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ions ook place smoo hly and ga e he poly (he )a yla ed p oduc s in modes o good yields (41 o 83%) in ela i ely sho eac ion imes. In gene al, elec on- ich bo onic acids ga e he highes yields (en ies 1–4, 9 and 11 in Table 1) and sho es eac ion imes. Speci ically, he bes esul s, bo h in yield (65 o 83%) and eac ion imes, we e ob ained using 2- hienylbo onic acid, since he eac ions ook only 20 min. While he elec on-poo bo onic acids equi ed longe eac ion imes (en ies 10 and 12 in Table 1). No clea end was obse ed when he meso-a yl subs i uen s we e modi ied. Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ion on 3a–e 1. En y A R-B(OH)2 Reac ion Time Yield 2 (%) Compound 1 S 20 min 80 4a 2 S 20 min 83 4b 3 S 20 min 65 4c 4 MeO S 25 min 76 4d 5 OHC S 2 h 55 4e 6 4 h 52 4 7 4 h 57 4g 8 F 3 C 5 h 41 4h 9 MeO 2 h 65 4i 10 MeOC 14 h 65 4j 11 MeO Me 3 Si 4 h 63 4k 12 MeO NC 16 h 57 4l 1 Condi ions: 3a (1 equi .), bo onic acid (8 equi .) Pd(OAc)2 (10 mol%), SPhos (22 mol%), K3PO4 (16 equi .) in PhCH3 a 90 °C oo no e. 2 Isola ed yield. 2.2. Pho ophysical P ope ies The a yla ion o he py oles ex ends he ch omopho ic delocalized π-sys em pushing he spec al bands owa ds he ed edge o he isible (abso p ion and emission o 4 and 4g placed a a ound 590 and 620 nm, espec i ely, Figu e 1). The meso-phenyl does no ake pa in he delocalized amewo k o he dipy in owing o i s wis ed geome ical a angemen ( heo e ically p edic ed o sion angle a ound 70° om g ound Molecules 2023, 28, x FOR PEER REVIEW 4 o 15 Nex , he key s ep o ou syn he ic plan was conduc ed, ha is, he mul iple unc ionaliza ion o he b omina ed posi ions ia he Suzuki–Miyau a c oss-coupling eac ion in 3a (Table S1). The eac ion condi ions used in en y 1 and 2 we e epo ed in he li e a u e o he mul iple unc ionaliza ion o BODIPYs [34,35]. Fo en y 1, he eac ion was incomple e, and mul iple p oduc s we e obse ed, while o en y 2, he desi ed p oduc 4 was isola ed in 42% yield. When we used Pd(OAc)2 and SPhos, along wi h K3PO4 as a base, he yield o 4 inc eased o 52% (en y 3 in Table S1). Once he bes condi ions we e de e mined, we se ou o eac 3a–e wi h se e al (he )a ylbo onic acids o di e en elec onic na u es o s udy he scope o he Suzuki– Miyau a c oss-coupling eac ion. The esul s ob ained o he mul iple unc ionaliza ion o 3a–e a e shown in Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ions ook place smoo hly and ga e he poly (he )a yla ed p oduc s in modes o good yields (41 o 83%) in ela i ely sho eac ion imes. In gene al, elec on- ich bo onic acids ga e he highes yields (en ies 1–4, 9 and 11 in Table 1) and sho es eac ion imes. Speci ically, he bes esul s, bo h in yield (65 o 83%) and eac ion imes, we e ob ained using 2- hienylbo onic acid, since he eac ions ook only 20 min. While he elec on-poo bo onic acids equi ed longe eac ion imes (en ies 10 and 12 in Table 1). No clea end was obse ed when he meso-a yl subs i uen s we e modi ied. Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ion on 3a–e 1. En y A R-B(OH)2 Reac ion Time Yield 2 (%) Compound 1 S 20 min 80 4a 2 S 20 min 83 4b 3 S 20 min 65 4c 4 MeO S 25 min 76 4d 5 OHC S 2 h 55 4e 6 4 h 52 4 7 4 h 57 4g 8 F 3 C 5 h 41 4h 9 MeO 2 h 65 4i 10 MeOC 14 h 65 4j 11 MeO Me 3 Si 4 h 63 4k 12 MeO NC 16 h 57 4l 1 Condi ions: 3a (1 equi .), bo onic acid (8 equi .) Pd(OAc)2 (10 mol%), SPhos (22 mol%), K3PO4 (16 equi .) in PhCH3 a 90 °C oo no e. 2 Isola ed yield. 2.2. Pho ophysical P ope ies The a yla ion o he py oles ex ends he ch omopho ic delocalized π-sys em pushing he spec al bands owa ds he ed edge o he isible (abso p ion and emission o 4 and 4g placed a a ound 590 and 620 nm, espec i ely, Figu e 1). The meso-phenyl does no ake pa in he delocalized amewo k o he dipy in owing o i s wis ed geome ical a angemen ( heo e ically p edic ed o sion angle a ound 70° om g ound 20 min 80 4a 2 Molecules 2023, 28, x FOR PEER REVIEW 4 o 15 Nex , he key s ep o ou syn he ic plan was conduc ed, ha is, he mul iple unc ionaliza ion o he b omina ed posi ions ia he Suzuki–Miyau a c oss-coupling eac ion in 3a (Table S1). The eac ion condi ions used in en y 1 and 2 we e epo ed in he li e a u e o he mul iple unc ionaliza ion o BODIPYs [34,35]. Fo en y 1, he eac ion was incomple e, and mul iple p oduc s we e obse ed, while o en y 2, he desi ed p oduc 4 was isola ed in 42% yield. When we used Pd(OAc)2 and SPhos, along wi h K3PO4 as a base, he yield o 4 inc eased o 52% (en y 3 in Table S1). Once he bes condi ions we e de e mined, we se ou o eac 3a–e wi h se e al (he )a ylbo onic acids o di e en elec onic na u es o s udy he scope o he Suzuki– Miyau a c oss-coupling eac ion. The esul s ob ained o he mul iple unc ionaliza ion o 3a–e a e shown in Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ions ook place smoo hly and ga e he poly (he )a yla ed p oduc s in modes o good yields (41 o 83%) in ela i ely sho eac ion imes. In gene al, elec on- ich bo onic acids ga e he highes yields (en ies 1–4, 9 and 11 in Table 1) and sho es eac ion imes. Speci ically, he bes esul s, bo h in yield (65 o 83%) and eac ion imes, we e ob ained using 2- hienylbo onic acid, since he eac ions ook only 20 min. While he elec on-poo bo onic acids equi ed longe eac ion imes (en ies 10 and 12 in Table 1). No clea end was obse ed when he meso-a yl subs i uen s we e modi ied. Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ion on 3a–e 1. En y A R-B(OH)2 Reac ion Time Yield 2 (%) Compound 1 S 20 min 80 4a 2 S 20 min 83 4b 3 S 20 min 65 4c 4 MeO S 25 min 76 4d 5 OHC S 2 h 55 4e 6 4 h 52 4 7 4 h 57 4g 8 F 3 C 5 h 41 4h 9 MeO 2 h 65 4i 10 MeOC 14 h 65 4j 11 MeO Me 3 Si 4 h 63 4k 12 MeO NC 16 h 57 4l 1 Condi ions: 3a (1 equi .), bo onic acid (8 equi .) Pd(OAc)2 (10 mol%), SPhos (22 mol%), K3PO4 (16 equi .) in PhCH3 a 90 °C oo no e. 2 Isola ed yield. 2.2. Pho ophysical P ope ies The a yla ion o he py oles ex ends he ch omopho ic delocalized π-sys em pushing he spec al bands owa ds he ed edge o he isible (abso p ion and emission o 4 and 4g placed a a ound 590 and 620 nm, espec i ely, Figu e 1). The meso-phenyl does no ake pa in he delocalized amewo k o he dipy in owing o i s wis ed geome ical a angemen ( heo e ically p edic ed o sion angle a ound 70° om g ound Molecules 2023, 28, x FOR PEER REVIEW 4 o 15 Nex , he key s ep o ou syn he ic plan was conduc ed, ha is, he mul iple unc ionaliza ion o he b omina ed posi ions ia he Suzuki–Miyau a c oss-coupling eac ion in 3a (Table S1). The eac ion condi ions used in en y 1 and 2 we e epo ed in he li e a u e o he mul iple unc ionaliza ion o BODIPYs [34,35]. Fo en y 1, he eac ion was incomple e, and mul iple p oduc s we e obse ed, while o en y 2, he desi ed p oduc 4 was isola ed in 42% yield. When we used Pd(OAc)2 and SPhos, along wi h K3PO4 as a base, he yield o 4 inc eased o 52% (en y 3 in Table S1). Once he bes condi ions we e de e mined, we se ou o eac 3a–e wi h se e al (he )a ylbo onic acids o di e en elec onic na u es o s udy he scope o he Suzuki– Miyau a c oss-coupling eac ion. The esul s ob ained o he mul iple unc ionaliza ion o 3a–e a e shown in Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ions ook place smoo hly and ga e he poly (he )a yla ed p oduc s in modes o good yields (41 o 83%) in ela i ely sho eac ion imes. In gene al, elec on- ich bo onic acids ga e he highes yields (en ies 1–4, 9 and 11 in Table 1) and sho es eac ion imes. Speci ically, he bes esul s, bo h in yield (65 o 83%) and eac ion imes, we e ob ained using 2- hienylbo onic acid, since he eac ions ook only 20 min. While he elec on-poo bo onic acids equi ed longe eac ion imes (en ies 10 and 12 in Table 1). No clea end was obse ed when he meso-a yl subs i uen s we e modi ied. Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ion on 3a–e 1. En y A R-B(OH)2 Reac ion Time Yield 2 (%) Compound 1 S 20 min 80 4a 2 S 20 min 83 4b 3 S 20 min 65 4c 4 MeO S 25 min 76 4d 5 OHC S 2 h 55 4e 6 4 h 52 4 7 4 h 57 4g 8 F 3 C 5 h 41 4h 9 MeO 2 h 65 4i 10 MeOC 14 h 65 4j 11 MeO Me 3 Si 4 h 63 4k 12 MeO NC 16 h 57 4l 1 Condi ions: 3a (1 equi .), bo onic acid (8 equi .) Pd(OAc)2 (10 mol%), SPhos (22 mol%), K3PO4 (16 equi .) in PhCH3 a 90 °C oo no e. 2 Isola ed yield. 2.2. Pho ophysical P ope ies The a yla ion o he py oles ex ends he ch omopho ic delocalized π-sys em pushing he spec al bands owa ds he ed edge o he isible (abso p ion and emission o 4 and 4g placed a a ound 590 and 620 nm, espec i ely, Figu e 1). The meso-phenyl does no ake pa in he delocalized amewo k o he dipy in owing o i s wis ed geome ical a angemen ( heo e ically p edic ed o sion angle a ound 70° om g ound 20 min 83 4b 3 Molecules 2023, 28, x FOR PEER REVIEW 4 o 15 Nex , he key s ep o ou syn he ic plan was conduc ed, ha is, he mul iple unc ionaliza ion o he b omina ed posi ions ia he Suzuki–Miyau a c oss-coupling eac ion in 3a (Table S1). The eac ion condi ions used in en y 1 and 2 we e epo ed in he li e a u e o he mul iple unc ionaliza ion o BODIPYs [34,35]. Fo en y 1, he eac ion was incomple e, and mul iple p oduc s we e obse ed, while o en y 2, he desi ed p oduc 4 was isola ed in 42% yield. When we used Pd(OAc)2 and SPhos, along wi h K3PO4 as a base, he yield o 4 inc eased o 52% (en y 3 in Table S1). Once he bes condi ions we e de e mined, we se ou o eac 3a–e wi h se e al (he )a ylbo onic acids o di e en elec onic na u es o s udy he scope o he Suzuki– Miyau a c oss-coupling eac ion. The esul s ob ained o he mul iple unc ionaliza ion o 3a–e a e shown in Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ions ook place smoo hly and ga e he poly (he )a yla ed p oduc s in modes o good yields (41 o 83%) in ela i ely sho eac ion imes. In gene al, elec on- ich bo onic acids ga e he highes yields (en ies 1–4, 9 and 11 in Table 1) and sho es eac ion imes. Speci ically, he bes esul s, bo h in yield (65 o 83%) and eac ion imes, we e ob ained using 2- hienylbo onic acid, since he eac ions ook only 20 min. While he elec on-poo bo onic acids equi ed longe eac ion imes (en ies 10 and 12 in Table 1). No clea end was obse ed when he meso-a yl subs i uen s we e modi ied. Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ion on 3a–e 1. En y A R-B(OH)2 Reac ion Time Yield 2 (%) Compound 1 S 20 min 80 4a 2 S 20 min 83 4b 3 S 20 min 65 4c 4 MeO S 25 min 76 4d 5 OHC S 2 h 55 4e 6 4 h 52 4 7 4 h 57 4g 8 F 3 C 5 h 41 4h 9 MeO 2 h 65 4i 10 MeOC 14 h 65 4j 11 MeO Me 3 Si 4 h 63 4k 12 MeO NC 16 h 57 4l 1 Condi ions: 3a (1 equi .), bo onic acid (8 equi .) Pd(OAc)2 (10 mol%), SPhos (22 mol%), K3PO4 (16 equi .) in PhCH3 a 90 °C oo no e. 2 Isola ed yield. 2.2. Pho ophysical P ope ies The a yla ion o he py oles ex ends he ch omopho ic delocalized π-sys em pushing he spec al bands owa ds he ed edge o he isible (abso p ion and emission o 4 and 4g placed a a ound 590 and 620 nm, espec i ely, Figu e 1). The meso-phenyl does no ake pa in he delocalized amewo k o he dipy in owing o i s wis ed geome ical a angemen ( heo e ically p edic ed o sion angle a ound 70° om g ound Molecules 2023, 28, x FOR PEER REVIEW 4 o 15 Nex , he key s ep o ou syn he ic plan was conduc ed, ha is, he mul iple unc ionaliza ion o he b omina ed posi ions ia he Suzuki–Miyau a c oss-coupling eac ion in 3a (Table S1). The eac ion condi ions used in en y 1 and 2 we e epo ed in he li e a u e o he mul iple unc ionaliza ion o BODIPYs [34,35]. Fo en y 1, he eac ion was incomple e, and mul iple p oduc s we e obse ed, while o en y 2, he desi ed p oduc 4 was isola ed in 42% yield. When we used Pd(OAc)2 and SPhos, along wi h K3PO4 as a base, he yield o 4 inc eased o 52% (en y 3 in Table S1). Once he bes condi ions we e de e mined, we se ou o eac 3a–e wi h se e al (he )a ylbo onic acids o di e en elec onic na u es o s udy he scope o he Suzuki– Miyau a c oss-coupling eac ion. The esul s ob ained o he mul iple unc ionaliza ion o 3a–e a e shown in Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ions ook place smoo hly and ga e he poly (he )a yla ed p oduc s in modes o good yields (41 o 83%) in ela i ely sho eac ion imes. In gene al, elec on- ich bo onic acids ga e he highes yields (en ies 1–4, 9 and 11 in Table 1) and sho es eac ion imes. Speci ically, he bes esul s, bo h in yield (65 o 83%) and eac ion imes, we e ob ained using 2- hienylbo onic acid, since he eac ions ook only 20 min. While he elec on-poo bo onic acids equi ed longe eac ion imes (en ies 10 and 12 in Table 1). No clea end was obse ed when he meso-a yl subs i uen s we e modi ied. Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ion on 3a–e 1. En y A R-B(OH)2 Reac ion Time Yield 2 (%) Compound 1 S 20 min 80 4a 2 S 20 min 83 4b 3 S 20 min 65 4c 4 MeO S 25 min 76 4d 5 OHC S 2 h 55 4e 6 4 h 52 4 7 4 h 57 4g 8 F 3 C 5 h 41 4h 9 MeO 2 h 65 4i 10 MeOC 14 h 65 4j 11 MeO Me 3 Si 4 h 63 4k 12 MeO NC 16 h 57 4l 1 Condi ions: 3a (1 equi .), bo onic acid (8 equi .) Pd(OAc)2 (10 mol%), SPhos (22 mol%), K3PO4 (16 equi .) in PhCH3 a 90 °C oo no e. 2 Isola ed yield. 2.2. Pho ophysical P ope ies The a yla ion o he py oles ex ends he ch omopho ic delocalized π-sys em pushing he spec al bands owa ds he ed edge o he isible (abso p ion and emission o 4 and 4g placed a a ound 590 and 620 nm, espec i ely, Figu e 1). The meso-phenyl does no ake pa in he delocalized amewo k o he dipy in owing o i s wis ed geome ical a angemen ( heo e ically p edic ed o sion angle a ound 70° om g ound 20 min 65 4c 4 Molecules 2023, 28, x FOR PEER REVIEW 4 o 15 Nex , he key s ep o ou syn he ic plan was conduc ed, ha is, he mul iple unc ionaliza ion o he b omina ed posi ions ia he Suzuki–Miyau a c oss-coupling eac ion in 3a (Table S1). The eac ion condi ions used in en y 1 and 2 we e epo ed in he li e a u e o he mul iple unc ionaliza ion o BODIPYs [34,35]. Fo en y 1, he eac ion was incomple e, and mul iple p oduc s we e obse ed, while o en y 2, he desi ed p oduc 4 was isola ed in 42% yield. When we used Pd(OAc)2 and SPhos, along wi h K3PO4 as a base, he yield o 4 inc eased o 52% (en y 3 in Table S1). Once he bes condi ions we e de e mined, we se ou o eac 3a–e wi h se e al (he )a ylbo onic acids o di e en elec onic na u es o s udy he scope o he Suzuki– Miyau a c oss-coupling eac ion. The esul s ob ained o he mul iple unc ionaliza ion o 3a–e a e shown in Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ions ook place smoo hly and ga e he poly (he )a yla ed p oduc s in modes o good yields (41 o 83%) in ela i ely sho eac ion imes. In gene al, elec on- ich bo onic acids ga e he highes yields (en ies 1–4, 9 and 11 in Table 1) and sho es eac ion imes. Speci ically, he bes esul s, bo h in yield (65 o 83%) and eac ion imes, we e ob ained using 2- hienylbo onic acid, since he eac ions ook only 20 min. While he elec on-poo bo onic acids equi ed longe eac ion imes (en ies 10 and 12 in Table 1). No clea end was obse ed when he meso-a yl subs i uen s we e modi ied. Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ion on 3a–e 1. En y A R-B(OH)2 Reac ion Time Yield 2 (%) Compound 1 S 20 min 80 4a 2 S 20 min 83 4b 3 S 20 min 65 4c 4 MeO S 25 min 76 4d 5 OHC S 2 h 55 4e 6 4 h 52 4 7 4 h 57 4g 8 F 3 C 5 h 41 4h 9 MeO 2 h 65 4i 10 MeOC 14 h 65 4j 11 MeO Me 3 Si 4 h 63 4k 12 MeO NC 16 h 57 4l 1 Condi ions: 3a (1 equi .), bo onic acid (8 equi .) Pd(OAc)2 (10 mol%), SPhos (22 mol%), K3PO4 (16 equi .) in PhCH3 a 90 °C oo no e. 2 Isola ed yield. 2.2. Pho ophysical P ope ies The a yla ion o he py oles ex ends he ch omopho ic delocalized π-sys em pushing he spec al bands owa ds he ed edge o he isible (abso p ion and emission o 4 and 4g placed a a ound 590 and 620 nm, espec i ely, Figu e 1). The meso-phenyl does no ake pa in he delocalized amewo k o he dipy in owing o i s wis ed geome ical a angemen ( heo e ically p edic ed o sion angle a ound 70° om g ound Molecules 2023, 28, x FOR PEER REVIEW 4 o 15 Nex , he key s ep o ou syn he ic plan was conduc ed, ha is, he mul iple unc ionaliza ion o he b omina ed posi ions ia he Suzuki–Miyau a c oss-coupling eac ion in 3a (Table S1). The eac ion condi ions used in en y 1 and 2 we e epo ed in he li e a u e o he mul iple unc ionaliza ion o BODIPYs [34,35]. Fo en y 1, he eac ion was incomple e, and mul iple p oduc s we e obse ed, while o en y 2, he desi ed p oduc 4 was isola ed in 42% yield. When we used Pd(OAc)2 and SPhos, along wi h K3PO4 as a base, he yield o 4 inc eased o 52% (en y 3 in Table S1). Once he bes condi ions we e de e mined, we se ou o eac 3a–e wi h se e al (he )a ylbo onic acids o di e en elec onic na u es o s udy he scope o he Suzuki– Miyau a c oss-coupling eac ion. The esul s ob ained o he mul iple unc ionaliza ion o 3a–e a e shown in Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ions ook place smoo hly and ga e he poly (he )a yla ed p oduc s in modes o good yields (41 o 83%) in ela i ely sho eac ion imes. In gene al, elec on- ich bo onic acids ga e he highes yields (en ies 1–4, 9 and 11 in Table 1) and sho es eac ion imes. Speci ically, he bes esul s, bo h in yield (65 o 83%) and eac ion imes, we e ob ained using 2- hienylbo onic acid, since he eac ions ook only 20 min. While he elec on-poo bo onic acids equi ed longe eac ion imes (en ies 10 and 12 in Table 1). No clea end was obse ed when he meso-a yl subs i uen s we e modi ied. Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ion on 3a–e 1. En y A R-B(OH)2 Reac ion Time Yield 2 (%) Compound 1 S 20 min 80 4a 2 S 20 min 83 4b 3 S 20 min 65 4c 4 MeO S 25 min 76 4d 5 OHC S 2 h 55 4e 6 4 h 52 4 7 4 h 57 4g 8 F 3 C 5 h 41 4h 9 MeO 2 h 65 4i 10 MeOC 14 h 65 4j 11 MeO Me 3 Si 4 h 63 4k 12 MeO NC 16 h 57 4l 1 Condi ions: 3a (1 equi .), bo onic acid (8 equi .) Pd(OAc)2 (10 mol%), SPhos (22 mol%), K3PO4 (16 equi .) in PhCH3 a 90 °C oo no e. 2 Isola ed yield. 2.2. Pho ophysical P ope ies The a yla ion o he py oles ex ends he ch omopho ic delocalized π-sys em pushing he spec al bands owa ds he ed edge o he isible (abso p ion and emission o 4 and 4g placed a a ound 590 and 620 nm, espec i ely, Figu e 1). The meso-phenyl does no ake pa in he delocalized amewo k o he dipy in owing o i s wis ed geome ical a angemen ( heo e ically p edic ed o sion angle a ound 70° om g ound 25 min 76 4d 5 Molecules 2023, 28, x FOR PEER REVIEW 4 o 15 Nex , he key s ep o ou syn he ic plan was conduc ed, ha is, he mul iple unc ionaliza ion o he b omina ed posi ions ia he Suzuki–Miyau a c oss-coupling eac ion in 3a (Table S1). The eac ion condi ions used in en y 1 and 2 we e epo ed in he li e a u e o he mul iple unc ionaliza ion o BODIPYs [34,35]. Fo en y 1, he eac ion was incomple e, and mul iple p oduc s we e obse ed, while o en y 2, he desi ed p oduc 4 was isola ed in 42% yield. When we used Pd(OAc)2 and SPhos, along wi h K3PO4 as a base, he yield o 4 inc eased o 52% (en y 3 in Table S1). Once he bes condi ions we e de e mined, we se ou o eac 3a–e wi h se e al (he )a ylbo onic acids o di e en elec onic na u es o s udy he scope o he Suzuki– Miyau a c oss-coupling eac ion. The esul s ob ained o he mul iple unc ionaliza ion o 3a–e a e shown in Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ions ook place smoo hly and ga e he poly (he )a yla ed p oduc s in modes o good yields (41 o 83%) in ela i ely sho eac ion imes. In gene al, elec on- ich bo onic acids ga e he highes yields (en ies 1–4, 9 and 11 in Table 1) and sho es eac ion imes. Speci ically, he bes esul s, bo h in yield (65 o 83%) and eac ion imes, we e ob ained using 2- hienylbo onic acid, since he eac ions ook only 20 min. While he elec on-poo bo onic acids equi ed longe eac ion imes (en ies 10 and 12 in Table 1). No clea end was obse ed when he meso-a yl subs i uen s we e modi ied. Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ion on 3a–e 1. En y A R-B(OH)2 Reac ion Time Yield 2 (%) Compound 1 S 20 min 80 4a 2 S 20 min 83 4b 3 S 20 min 65 4c 4 MeO S 25 min 76 4d 5 OHC S 2 h 55 4e 6 4 h 52 4 7 4 h 57 4g 8 F 3 C 5 h 41 4h 9 MeO 2 h 65 4i 10 MeOC 14 h 65 4j 11 MeO Me 3 Si 4 h 63 4k 12 MeO NC 16 h 57 4l 1 Condi ions: 3a (1 equi .), bo onic acid (8 equi .) Pd(OAc)2 (10 mol%), SPhos (22 mol%), K3PO4 (16 equi .) in PhCH3 a 90 °C oo no e. 2 Isola ed yield. 2.2. Pho ophysical P ope ies The a yla ion o he py oles ex ends he ch omopho ic delocalized π-sys em pushing he spec al bands owa ds he ed edge o he isible (abso p ion and emission o 4 and 4g placed a a ound 590 and 620 nm, espec i ely, Figu e 1). The meso-phenyl does no ake pa in he delocalized amewo k o he dipy in owing o i s wis ed geome ical a angemen ( heo e ically p edic ed o sion angle a ound 70° om g ound Molecules 2023, 28, x FOR PEER REVIEW 4 o 15 Nex , he key s ep o ou syn he ic plan was conduc ed, ha is, he mul iple unc ionaliza ion o he b omina ed posi ions ia he Suzuki–Miyau a c oss-coupling eac ion in 3a (Table S1). The eac ion condi ions used in en y 1 and 2 we e epo ed in he li e a u e o he mul iple unc ionaliza ion o BODIPYs [34,35]. Fo en y 1, he eac ion was incomple e, and mul iple p oduc s we e obse ed, while o en y 2, he desi ed p oduc 4 was isola ed in 42% yield. When we used Pd(OAc)2 and SPhos, along wi h K3PO4 as a base, he yield o 4 inc eased o 52% (en y 3 in Table S1). Once he bes condi ions we e de e mined, we se ou o eac 3a–e wi h se e al (he )a ylbo onic acids o di e en elec onic na u es o s udy he scope o he Suzuki– Miyau a c oss-coupling eac ion. The esul s ob ained o he mul iple unc ionaliza ion o 3a–e a e shown in Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ions ook place smoo hly and ga e he poly (he )a yla ed p oduc s in modes o good yields (41 o 83%) in ela i ely sho eac ion imes. In gene al, elec on- ich bo onic acids ga e he highes yields (en ies 1–4, 9 and 11 in Table 1) and sho es eac ion imes. Speci ically, he bes esul s, bo h in yield (65 o 83%) and eac ion imes, we e ob ained using 2- hienylbo onic acid, since he eac ions ook only 20 min. While he elec on-poo bo onic acids equi ed longe eac ion imes (en ies 10 and 12 in Table 1). No clea end was obse ed when he meso-a yl subs i uen s we e modi ied. Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ion on 3a–e 1. En y A R-B(OH)2 Reac ion Time Yield 2 (%) Compound 1 S 20 min 80 4a 2 S 20 min 83 4b 3 S 20 min 65 4c 4 MeO S 25 min 76 4d 5 OHC S 2 h 55 4e 6 4 h 52 4 7 4 h 57 4g 8 F 3 C 5 h 41 4h 9 MeO 2 h 65 4i 10 MeOC 14 h 65 4j 11 MeO Me 3 Si 4 h 63 4k 12 MeO NC 16 h 57 4l 1 Condi ions: 3a (1 equi .), bo onic acid (8 equi .) Pd(OAc)2 (10 mol%), SPhos (22 mol%), K3PO4 (16 equi .) in PhCH3 a 90 °C oo no e. 2 Isola ed yield. 2.2. Pho ophysical P ope ies The a yla ion o he py oles ex ends he ch omopho ic delocalized π-sys em pushing he spec al bands owa ds he ed edge o he isible (abso p ion and emission o 4 and 4g placed a a ound 590 and 620 nm, espec i ely, Figu e 1). The meso-phenyl does no ake pa in he delocalized amewo k o he dipy in owing o i s wis ed geome ical a angemen ( heo e ically p edic ed o sion angle a ound 70° om g ound 2 h 55 4e 6 Molecules 2023, 28, x FOR PEER REVIEW 4 o 15 Nex , he key s ep o ou syn he ic plan was conduc ed, ha is, he mul iple unc ionaliza ion o he b omina ed posi ions ia he Suzuki–Miyau a c oss-coupling eac ion in 3a (Table S1). The eac ion condi ions used in en y 1 and 2 we e epo ed in he li e a u e o he mul iple unc ionaliza ion o BODIPYs [34,35]. Fo en y 1, he eac ion was incomple e, and mul iple p oduc s we e obse ed, while o en y 2, he desi ed p oduc 4 was isola ed in 42% yield. When we used Pd(OAc)2 and SPhos, along wi h K3PO4 as a base, he yield o 4 inc eased o 52% (en y 3 in Table S1). Once he bes condi ions we e de e mined, we se ou o eac 3a–e wi h se e al (he )a ylbo onic acids o di e en elec onic na u es o s udy he scope o he Suzuki– Miyau a c oss-coupling eac ion. The esul s ob ained o he mul iple unc ionaliza ion o 3a–e a e shown in Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ions ook place smoo hly and ga e he poly (he )a yla ed p oduc s in modes o good yields (41 o 83%) in ela i ely sho eac ion imes. In gene al, elec on- ich bo onic acids ga e he highes yields (en ies 1–4, 9 and 11 in Table 1) and sho es eac ion imes. Speci ically, he bes esul s, bo h in yield (65 o 83%) and eac ion imes, we e ob ained using 2- hienylbo onic acid, since he eac ions ook only 20 min. While he elec on-poo bo onic acids equi ed longe eac ion imes (en ies 10 and 12 in Table 1). No clea end was obse ed when he meso-a yl subs i uen s we e modi ied. Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ion on 3a–e 1. En y A R-B(OH)2 Reac ion Time Yield 2 (%) Compound 1 S 20 min 80 4a 2 S 20 min 83 4b 3 S 20 min 65 4c 4 MeO S 25 min 76 4d 5 OHC S 2 h 55 4e 6 4 h 52 4 7 4 h 57 4g 8 F 3 C 5 h 41 4h 9 MeO 2 h 65 4i 10 MeOC 14 h 65 4j 11 MeO Me 3 Si 4 h 63 4k 12 MeO NC 16 h 57 4l 1 Condi ions: 3a (1 equi .), bo onic acid (8 equi .) Pd(OAc)2 (10 mol%), SPhos (22 mol%), K3PO4 (16 equi .) in PhCH3 a 90 °C oo no e. 2 Isola ed yield. 2.2. Pho ophysical P ope ies The a yla ion o he py oles ex ends he ch omopho ic delocalized π-sys em pushing he spec al bands owa ds he ed edge o he isible (abso p ion and emission o 4 and 4g placed a a ound 590 and 620 nm, espec i ely, Figu e 1). The meso-phenyl does no ake pa in he delocalized amewo k o he dipy in owing o i s wis ed geome ical a angemen ( heo e ically p edic ed o sion angle a ound 70° om g ound Molecules 2023, 28, x FOR PEER REVIEW 4 o 15 Nex , he key s ep o ou syn he ic plan was conduc ed, ha is, he mul iple unc ionaliza ion o he b omina ed posi ions ia he Suzuki–Miyau a c oss-coupling eac ion in 3a (Table S1). The eac ion condi ions used in en y 1 and 2 we e epo ed in he li e a u e o he mul iple unc ionaliza ion o BODIPYs [34,35]. Fo en y 1, he eac ion was incomple e, and mul iple p oduc s we e obse ed, while o en y 2, he desi ed p oduc 4 was isola ed in 42% yield. When we used Pd(OAc)2 and SPhos, along wi h K3PO4 as a base, he yield o 4 inc eased o 52% (en y 3 in Table S1). Once he bes condi ions we e de e mined, we se ou o eac 3a–e wi h se e al (he )a ylbo onic acids o di e en elec onic na u es o s udy he scope o he Suzuki– Miyau a c oss-coupling eac ion. The esul s ob ained o he mul iple unc ionaliza ion o 3a–e a e shown in Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ions ook place smoo hly and ga e he poly (he )a yla ed p oduc s in modes o good yields (41 o 83%) in ela i ely sho eac ion imes. In gene al, elec on- ich bo onic acids ga e he highes yields (en ies 1–4, 9 and 11 in Table 1) and sho es eac ion imes. Speci ically, he bes esul s, bo h in yield (65 o 83%) and eac ion imes, we e ob ained using 2- hienylbo onic acid, since he eac ions ook only 20 min. While he elec on-poo bo onic acids equi ed longe eac ion imes (en ies 10 and 12 in Table 1). No clea end was obse ed when he meso-a yl subs i uen s we e modi ied. Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ion on 3a–e 1. En y A R-B(OH)2 Reac ion Time Yield 2 (%) Compound 1 S 20 min 80 4a 2 S 20 min 83 4b 3 S 20 min 65 4c 4 MeO S 25 min 76 4d 5 OHC S 2 h 55 4e 6 4 h 52 4 7 4 h 57 4g 8 F 3 C 5 h 41 4h 9 MeO 2 h 65 4i 10 MeOC 14 h 65 4j 11 MeO Me 3 Si 4 h 63 4k 12 MeO NC 16 h 57 4l 1 Condi ions: 3a (1 equi .), bo onic acid (8 equi .) Pd(OAc)2 (10 mol%), SPhos (22 mol%), K3PO4 (16 equi .) in PhCH3 a 90 °C oo no e. 2 Isola ed yield. 2.2. Pho ophysical P ope ies The a yla ion o he py oles ex ends he ch omopho ic delocalized π-sys em pushing he spec al bands owa ds he ed edge o he isible (abso p ion and emission o 4 and 4g placed a a ound 590 and 620 nm, espec i ely, Figu e 1). The meso-phenyl does no ake pa in he delocalized amewo k o he dipy in owing o i s wis ed geome ical a angemen ( heo e ically p edic ed o sion angle a ound 70° om g ound 4 h 52 4 7 Molecules 2023, 28, x FOR PEER REVIEW 4 o 15 Nex , he key s ep o ou syn he ic plan was conduc ed, ha is, he mul iple unc ionaliza ion o he b omina ed posi ions ia he Suzuki–Miyau a c oss-coupling eac ion in 3a (Table S1). The eac ion condi ions used in en y 1 and 2 we e epo ed in he li e a u e o he mul iple unc ionaliza ion o BODIPYs [34,35]. Fo en y 1, he eac ion was incomple e, and mul iple p oduc s we e obse ed, while o en y 2, he desi ed p oduc 4 was isola ed in 42% yield. When we used Pd(OAc)2 and SPhos, along wi h K3PO4 as a base, he yield o 4 inc eased o 52% (en y 3 in Table S1). Once he bes condi ions we e de e mined, we se ou o eac 3a–e wi h se e al (he )a ylbo onic acids o di e en elec onic na u es o s udy he scope o he Suzuki– Miyau a c oss-coupling eac ion. The esul s ob ained o he mul iple unc ionaliza ion o 3a–e a e shown in Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ions ook place smoo hly and ga e he poly (he )a yla ed p oduc s in modes o good yields (41 o 83%) in ela i ely sho eac ion imes. In gene al, elec on- ich bo onic acids ga e he highes yields (en ies 1–4, 9 and 11 in Table 1) and sho es eac ion imes. Speci ically, he bes esul s, bo h in yield (65 o 83%) and eac ion imes, we e ob ained using 2- hienylbo onic acid, since he eac ions ook only 20 min. While he elec on-poo bo onic acids equi ed longe eac ion imes (en ies 10 and 12 in Table 1). No clea end was obse ed when he meso-a yl subs i uen s we e modi ied. Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ion on 3a–e 1. En y A R-B(OH)2 Reac ion Time Yield 2 (%) Compound 1 S 20 min 80 4a 2 S 20 min 83 4b 3 S 20 min 65 4c 4 MeO S 25 min 76 4d 5 OHC S 2 h 55 4e 6 4 h 52 4 7 4 h 57 4g 8 F 3 C 5 h 41 4h 9 MeO 2 h 65 4i 10 MeOC 14 h 65 4j 11 MeO Me 3 Si 4 h 63 4k 12 MeO NC 16 h 57 4l 1 Condi ions: 3a (1 equi .), bo onic acid (8 equi .) Pd(OAc)2 (10 mol%), SPhos (22 mol%), K3PO4 (16 equi .) in PhCH3 a 90 °C oo no e. 2 Isola ed yield. 2.2. Pho ophysical P ope ies The a yla ion o he py oles ex ends he ch omopho ic delocalized π-sys em pushing he spec al bands owa ds he ed edge o he isible (abso p ion and emission o 4 and 4g placed a a ound 590 and 620 nm, espec i ely, Figu e 1). The meso-phenyl does no ake pa in he delocalized amewo k o he dipy in owing o i s wis ed geome ical a angemen ( heo e ically p edic ed o sion angle a ound 70° om g ound Molecules 2023, 28, x FOR PEER REVIEW 4 o 15 Nex , he key s ep o ou syn he ic plan was conduc ed, ha is, he mul iple unc ionaliza ion o he b omina ed posi ions ia he Suzuki–Miyau a c oss-coupling eac ion in 3a (Table S1). The eac ion condi ions used in en y 1 and 2 we e epo ed in he li e a u e o he mul iple unc ionaliza ion o BODIPYs [34,35]. Fo en y 1, he eac ion was incomple e, and mul iple p oduc s we e obse ed, while o en y 2, he desi ed p oduc 4 was isola ed in 42% yield. When we used Pd(OAc)2 and SPhos, along wi h K3PO4 as a base, he yield o 4 inc eased o 52% (en y 3 in Table S1). Once he bes condi ions we e de e mined, we se ou o eac 3a–e wi h se e al (he )a ylbo onic acids o di e en elec onic na u es o s udy he scope o he Suzuki– Miyau a c oss-coupling eac ion. The esul s ob ained o he mul iple unc ionaliza ion o 3a–e a e shown in Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ions ook place smoo hly and ga e he poly (he )a yla ed p oduc s in modes o good yields (41 o 83%) in ela i ely sho eac ion imes. In gene al, elec on- ich bo onic acids ga e he highes yields (en ies 1–4, 9 and 11 in Table 1) and sho es eac ion imes. Speci ically, he bes esul s, bo h in yield (65 o 83%) and eac ion imes, we e ob ained using 2- hienylbo onic acid, since he eac ions ook only 20 min. While he elec on-poo bo onic acids equi ed longe eac ion imes (en ies 10 and 12 in Table 1). No clea end was obse ed when he meso-a yl subs i uen s we e modi ied. Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ion on 3a–e 1. En y A R-B(OH)2 Reac ion Time Yield 2 (%) Compound 1 S 20 min 80 4a 2 S 20 min 83 4b 3 S 20 min 65 4c 4 MeO S 25 min 76 4d 5 OHC S 2 h 55 4e 6 4 h 52 4 7 4 h 57 4g 8 F 3 C 5 h 41 4h 9 MeO 2 h 65 4i 10 MeOC 14 h 65 4j 11 MeO Me 3 Si 4 h 63 4k 12 MeO NC 16 h 57 4l 1 Condi ions: 3a (1 equi .), bo onic acid (8 equi .) Pd(OAc)2 (10 mol%), SPhos (22 mol%), K3PO4 (16 equi .) in PhCH3 a 90 °C oo no e. 2 Isola ed yield. 2.2. Pho ophysical P ope ies The a yla ion o he py oles ex ends he ch omopho ic delocalized π-sys em pushing he spec al bands owa ds he ed edge o he isible (abso p ion and emission o 4 and 4g placed a a ound 590 and 620 nm, espec i ely, Figu e 1). The meso-phenyl does no ake pa in he delocalized amewo k o he dipy in owing o i s wis ed geome ical a angemen ( heo e ically p edic ed o sion angle a ound 70° om g ound 4 h 57 4g 8 Molecules 2023, 28, x FOR PEER REVIEW 4 o 15 Nex , he key s ep o ou syn he ic plan was conduc ed, ha is, he mul iple unc ionaliza ion o he b omina ed posi ions ia he Suzuki–Miyau a c oss-coupling eac ion in 3a (Table S1). The eac ion condi ions used in en y 1 and 2 we e epo ed in he li e a u e o he mul iple unc ionaliza ion o BODIPYs [34,35]. Fo en y 1, he eac ion was incomple e, and mul iple p oduc s we e obse ed, while o en y 2, he desi ed p oduc 4 was isola ed in 42% yield. When we used Pd(OAc)2 and SPhos, along wi h K3PO4 as a base, he yield o 4 inc eased o 52% (en y 3 in Table S1). Once he bes condi ions we e de e mined, we se ou o eac 3a–e wi h se e al (he )a ylbo onic acids o di e en elec onic na u es o s udy he scope o he Suzuki– Miyau a c oss-coupling eac ion. The esul s ob ained o he mul iple unc ionaliza ion o 3a–e a e shown in Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ions ook place smoo hly and ga e he poly (he )a yla ed p oduc s in modes o good yields (41 o 83%) in ela i ely sho eac ion imes. In gene al, elec on- ich bo onic acids ga e he highes yields (en ies 1–4, 9 and 11 in Table 1) and sho es eac ion imes. Speci ically, he bes esul s, bo h in yield (65 o 83%) and eac ion imes, we e ob ained using 2- hienylbo onic acid, since he eac ions ook only 20 min. While he elec on-poo bo onic acids equi ed longe eac ion imes (en ies 10 and 12 in Table 1). No clea end was obse ed when he meso-a yl subs i uen s we e modi ied. Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ion on 3a–e 1. En y A R-B(OH)2 Reac ion Time Yield 2 (%) Compound 1 S 20 min 80 4a 2 S 20 min 83 4b 3 S 20 min 65 4c 4 MeO S 25 min 76 4d 5 OHC S 2 h 55 4e 6 4 h 52 4 7 4 h 57 4g 8 F 3 C 5 h 41 4h 9 MeO 2 h 65 4i 10 MeOC 14 h 65 4j 11 MeO Me 3 Si 4 h 63 4k 12 MeO NC 16 h 57 4l 1 Condi ions: 3a (1 equi .), bo onic acid (8 equi .) Pd(OAc)2 (10 mol%), SPhos (22 mol%), K3PO4 (16 equi .) in PhCH3 a 90 °C oo no e. 2 Isola ed yield. 2.2. Pho ophysical P ope ies The a yla ion o he py oles ex ends he ch omopho ic delocalized π-sys em pushing he spec al bands owa ds he ed edge o he isible (abso p ion and emission o 4 and 4g placed a a ound 590 and 620 nm, espec i ely, Figu e 1). The meso-phenyl does no ake pa in he delocalized amewo k o he dipy in owing o i s wis ed geome ical a angemen ( heo e ically p edic ed o sion angle a ound 70° om g ound Molecules 2023, 28, x FOR PEER REVIEW 4 o 15 Nex , he key s ep o ou syn he ic plan was conduc ed, ha is, he mul iple unc ionaliza ion o he b omina ed posi ions ia he Suzuki–Miyau a c oss-coupling eac ion in 3a (Table S1). The eac ion condi ions used in en y 1 and 2 we e epo ed in he li e a u e o he mul iple unc ionaliza ion o BODIPYs [34,35]. Fo en y 1, he eac ion was incomple e, and mul iple p oduc s we e obse ed, while o en y 2, he desi ed p oduc 4 was isola ed in 42% yield. When we used Pd(OAc)2 and SPhos, along wi h K3PO4 as a base, he yield o 4 inc eased o 52% (en y 3 in Table S1). Once he bes condi ions we e de e mined, we se ou o eac 3a–e wi h se e al (he )a ylbo onic acids o di e en elec onic na u es o s udy he scope o he Suzuki– Miyau a c oss-coupling eac ion. The esul s ob ained o he mul iple unc ionaliza ion o 3a–e a e shown in Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ions ook place smoo hly and ga e he poly (he )a yla ed p oduc s in modes o good yields (41 o 83%) in ela i ely sho eac ion imes. In gene al, elec on- ich bo onic acids ga e he highes yields (en ies 1–4, 9 and 11 in Table 1) and sho es eac ion imes. Speci ically, he bes esul s, bo h in yield (65 o 83%) and eac ion imes, we e ob ained using 2- hienylbo onic acid, since he eac ions ook only 20 min. While he elec on-poo bo onic acids equi ed longe eac ion imes (en ies 10 and 12 in Table 1). No clea end was obse ed when he meso-a yl subs i uen s we e modi ied. Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ion on 3a–e 1. En y A R-B(OH)2 Reac ion Time Yield 2 (%) Compound 1 S 20 min 80 4a 2 S 20 min 83 4b 3 S 20 min 65 4c 4 MeO S 25 min 76 4d 5 OHC S 2 h 55 4e 6 4 h 52 4 7 4 h 57 4g 8 F 3 C 5 h 41 4h 9 MeO 2 h 65 4i 10 MeOC 14 h 65 4j 11 MeO Me 3 Si 4 h 63 4k 12 MeO NC 16 h 57 4l 1 Condi ions: 3a (1 equi .), bo onic acid (8 equi .) Pd(OAc)2 (10 mol%), SPhos (22 mol%), K3PO4 (16 equi .) in PhCH3 a 90 °C oo no e. 2 Isola ed yield. 2.2. Pho ophysical P ope ies The a yla ion o he py oles ex ends he ch omopho ic delocalized π-sys em pushing he spec al bands owa ds he ed edge o he isible (abso p ion and emission o 4 and 4g placed a a ound 590 and 620 nm, espec i ely, Figu e 1). The meso-phenyl does no ake pa in he delocalized amewo k o he dipy in owing o i s wis ed geome ical a angemen ( heo e ically p edic ed o sion angle a ound 70° om g ound 5 h 41 4h 9 Molecules 2023, 28, x FOR PEER REVIEW 4 o 15 Nex , he key s ep o ou syn he ic plan was conduc ed, ha is, he mul iple unc ionaliza ion o he b omina ed posi ions ia he Suzuki–Miyau a c oss-coupling eac ion in 3a (Table S1). The eac ion condi ions used in en y 1 and 2 we e epo ed in he li e a u e o he mul iple unc ionaliza ion o BODIPYs [34,35]. Fo en y 1, he eac ion was incomple e, and mul iple p oduc s we e obse ed, while o en y 2, he desi ed p oduc 4 was isola ed in 42% yield. When we used Pd(OAc)2 and SPhos, along wi h K3PO4 as a base, he yield o 4 inc eased o 52% (en y 3 in Table S1). Once he bes condi ions we e de e mined, we se ou o eac 3a–e wi h se e al (he )a ylbo onic acids o di e en elec onic na u es o s udy he scope o he Suzuki– Miyau a c oss-coupling eac ion. The esul s ob ained o he mul iple unc ionaliza ion o 3a–e a e shown in Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ions ook place smoo hly and ga e he poly (he )a yla ed p oduc s in modes o good yields (41 o 83%) in ela i ely sho eac ion imes. In gene al, elec on- ich bo onic acids ga e he highes yields (en ies 1–4, 9 and 11 in Table 1) and sho es eac ion imes. Speci ically, he bes esul s, bo h in yield (65 o 83%) and eac ion imes, we e ob ained using 2- hienylbo onic acid, since he eac ions ook only 20 min. While he elec on-poo bo onic acids equi ed longe eac ion imes (en ies 10 and 12 in Table 1). No clea end was obse ed when he meso-a yl subs i uen s we e modi ied. Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ion on 3a–e 1. En y A R-B(OH)2 Reac ion Time Yield 2 (%) Compound 1 S 20 min 80 4a 2 S 20 min 83 4b 3 S 20 min 65 4c 4 MeO S 25 min 76 4d 5 OHC S 2 h 55 4e 6 4 h 52 4 7 4 h 57 4g 8 F 3 C 5 h 41 4h 9 MeO 2 h 65 4i 10 MeOC 14 h 65 4j 11 MeO Me 3 Si 4 h 63 4k 12 MeO NC 16 h 57 4l 1 Condi ions: 3a (1 equi .), bo onic acid (8 equi .) Pd(OAc)2 (10 mol%), SPhos (22 mol%), K3PO4 (16 equi .) in PhCH3 a 90 °C oo no e. 2 Isola ed yield. 2.2. Pho ophysical P ope ies The a yla ion o he py oles ex ends he ch omopho ic delocalized π-sys em pushing he spec al bands owa ds he ed edge o he isible (abso p ion and emission o 4 and 4g placed a a ound 590 and 620 nm, espec i ely, Figu e 1). The meso-phenyl does no ake pa in he delocalized amewo k o he dipy in owing o i s wis ed geome ical a angemen ( heo e ically p edic ed o sion angle a ound 70° om g ound Molecules 2023, 28, x FOR PEER REVIEW 4 o 15 Nex , he key s ep o ou syn he ic plan was conduc ed, ha is, he mul iple unc ionaliza ion o he b omina ed posi ions ia he Suzuki–Miyau a c oss-coupling eac ion in 3a (Table S1). The eac ion condi ions used in en y 1 and 2 we e epo ed in he li e a u e o he mul iple unc ionaliza ion o BODIPYs [34,35]. Fo en y 1, he eac ion was incomple e, and mul iple p oduc s we e obse ed, while o en y 2, he desi ed p oduc 4 was isola ed in 42% yield. When we used Pd(OAc)2 and SPhos, along wi h K3PO4 as a base, he yield o 4 inc eased o 52% (en y 3 in Table S1). Once he bes condi ions we e de e mined, we se ou o eac 3a–e wi h se e al (he )a ylbo onic acids o di e en elec onic na u es o s udy he scope o he Suzuki– Miyau a c oss-coupling eac ion. The esul s ob ained o he mul iple unc ionaliza ion o 3a–e a e shown in Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ions ook place smoo hly and ga e he poly (he )a yla ed p oduc s in modes o good yields (41 o 83%) in ela i ely sho eac ion imes. In gene al, elec on- ich bo onic acids ga e he highes yields (en ies 1–4, 9 and 11 in Table 1) and sho es eac ion imes. Speci ically, he bes esul s, bo h in yield (65 o 83%) and eac ion imes, we e ob ained using 2- hienylbo onic acid, since he eac ions ook only 20 min. While he elec on-poo bo onic acids equi ed longe eac ion imes (en ies 10 and 12 in Table 1). No clea end was obse ed when he meso-a yl subs i uen s we e modi ied. Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ion on 3a–e 1. En y A R-B(OH)2 Reac ion Time Yield 2 (%) Compound 1 S 20 min 80 4a 2 S 20 min 83 4b 3 S 20 min 65 4c 4 MeO S 25 min 76 4d 5 OHC S 2 h 55 4e 6 4 h 52 4 7 4 h 57 4g 8 F 3 C 5 h 41 4h 9 MeO 2 h 65 4i 10 MeOC 14 h 65 4j 11 MeO Me 3 Si 4 h 63 4k 12 MeO NC 16 h 57 4l 1 Condi ions: 3a (1 equi .), bo onic acid (8 equi .) Pd(OAc)2 (10 mol%), SPhos (22 mol%), K3PO4 (16 equi .) in PhCH3 a 90 °C oo no e. 2 Isola ed yield. 2.2. Pho ophysical P ope ies The a yla ion o he py oles ex ends he ch omopho ic delocalized π-sys em pushing he spec al bands owa ds he ed edge o he isible (abso p ion and emission o 4 and 4g placed a a ound 590 and 620 nm, espec i ely, Figu e 1). The meso-phenyl does no ake pa in he delocalized amewo k o he dipy in owing o i s wis ed geome ical a angemen ( heo e ically p edic ed o sion angle a ound 70° om g ound 2 h 65 4i 10 Molecules 2023, 28, x FOR PEER REVIEW 4 o 15 Nex , he key s ep o ou syn he ic plan was conduc ed, ha is, he mul iple unc ionaliza ion o he b omina ed posi ions ia he Suzuki–Miyau a c oss-coupling eac ion in 3a (Table S1). The eac ion condi ions used in en y 1 and 2 we e epo ed in he li e a u e o he mul iple unc ionaliza ion o BODIPYs [34,35]. Fo en y 1, he eac ion was incomple e, and mul iple p oduc s we e obse ed, while o en y 2, he desi ed p oduc 4 was isola ed in 42% yield. When we used Pd(OAc)2 and SPhos, along wi h K3PO4 as a base, he yield o 4 inc eased o 52% (en y 3 in Table S1). Once he bes condi ions we e de e mined, we se ou o eac 3a–e wi h se e al (he )a ylbo onic acids o di e en elec onic na u es o s udy he scope o he Suzuki– Miyau a c oss-coupling eac ion. The esul s ob ained o he mul iple unc ionaliza ion o 3a–e a e shown in Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ions ook place smoo hly and ga e he poly (he )a yla ed p oduc s in modes o good yields (41 o 83%) in ela i ely sho eac ion imes. In gene al, elec on- ich bo onic acids ga e he highes yields (en ies 1–4, 9 and 11 in Table 1) and sho es eac ion imes. Speci ically, he bes esul s, bo h in yield (65 o 83%) and eac ion imes, we e ob ained using 2- hienylbo onic acid, since he eac ions ook only 20 min. While he elec on-poo bo onic acids equi ed longe eac ion imes (en ies 10 and 12 in Table 1). No clea end was obse ed when he meso-a yl subs i uen s we e modi ied. Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ion on 3a–e 1. En y A R-B(OH)2 Reac ion Time Yield 2 (%) Compound 1 S 20 min 80 4a 2 S 20 min 83 4b 3 S 20 min 65 4c 4 MeO S 25 min 76 4d 5 OHC S 2 h 55 4e 6 4 h 52 4 7 4 h 57 4g 8 F 3 C 5 h 41 4h 9 MeO 2 h 65 4i 10 MeOC 14 h 65 4j 11 MeO Me 3 Si 4 h 63 4k 12 MeO NC 16 h 57 4l 1 Condi ions: 3a (1 equi .), bo onic acid (8 equi .) Pd(OAc)2 (10 mol%), SPhos (22 mol%), K3PO4 (16 equi .) in PhCH3 a 90 °C oo no e. 2 Isola ed yield. 2.2. Pho ophysical P ope ies The a yla ion o he py oles ex ends he ch omopho ic delocalized π-sys em pushing he spec al bands owa ds he ed edge o he isible (abso p ion and emission o 4 and 4g placed a a ound 590 and 620 nm, espec i ely, Figu e 1). The meso-phenyl does no ake pa in he delocalized amewo k o he dipy in owing o i s wis ed geome ical a angemen ( heo e ically p edic ed o sion angle a ound 70° om g ound Molecules 2023, 28, x FOR PEER REVIEW 4 o 15 Nex , he key s ep o ou syn he ic plan was conduc ed, ha is, he mul iple unc ionaliza ion o he b omina ed posi ions ia he Suzuki–Miyau a c oss-coupling eac ion in 3a (Table S1). The eac ion condi ions used in en y 1 and 2 we e epo ed in he li e a u e o he mul iple unc ionaliza ion o BODIPYs [34,35]. Fo en y 1, he eac ion was incomple e, and mul iple p oduc s we e obse ed, while o en y 2, he desi ed p oduc 4 was isola ed in 42% yield. When we used Pd(OAc)2 and SPhos, along wi h K3PO4 as a base, he yield o 4 inc eased o 52% (en y 3 in Table S1). Once he bes condi ions we e de e mined, we se ou o eac 3a–e wi h se e al (he )a ylbo onic acids o di e en elec onic na u es o s udy he scope o he Suzuki– Miyau a c oss-coupling eac ion. The esul s ob ained o he mul iple unc ionaliza ion o 3a–e a e shown in Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ions ook place smoo hly and ga e he poly (he )a yla ed p oduc s in modes o good yields (41 o 83%) in ela i ely sho eac ion imes. In gene al, elec on- ich bo onic acids ga e he highes yields (en ies 1–4, 9 and 11 in Table 1) and sho es eac ion imes. Speci ically, he bes esul s, bo h in yield (65 o 83%) and eac ion imes, we e ob ained using 2- hienylbo onic acid, since he eac ions ook only 20 min. While he elec on-poo bo onic acids equi ed longe eac ion imes (en ies 10 and 12 in Table 1). No clea end was obse ed when he meso-a yl subs i uen s we e modi ied. Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ion on 3a–e 1. En y A R-B(OH)2 Reac ion Time Yield 2 (%) Compound 1 S 20 min 80 4a 2 S 20 min 83 4b 3 S 20 min 65 4c 4 MeO S 25 min 76 4d 5 OHC S 2 h 55 4e 6 4 h 52 4 7 4 h 57 4g 8 F 3 C 5 h 41 4h 9 MeO 2 h 65 4i 10 MeOC 14 h 65 4j 11 MeO Me 3 Si 4 h 63 4k 12 MeO NC 16 h 57 4l 1 Condi ions: 3a (1 equi .), bo onic acid (8 equi .) Pd(OAc)2 (10 mol%), SPhos (22 mol%), K3PO4 (16 equi .) in PhCH3 a 90 °C oo no e. 2 Isola ed yield. 2.2. Pho ophysical P ope ies The a yla ion o he py oles ex ends he ch omopho ic delocalized π-sys em pushing he spec al bands owa ds he ed edge o he isible (abso p ion and emission o 4 and 4g placed a a ound 590 and 620 nm, espec i ely, Figu e 1). The meso-phenyl does no ake pa in he delocalized amewo k o he dipy in owing o i s wis ed geome ical a angemen ( heo e ically p edic ed o sion angle a ound 70° om g ound 14 h 65 4j 11 Molecules 2023, 28, x FOR PEER REVIEW 4 o 15 Nex , he key s ep o ou syn he ic plan was conduc ed, ha is, he mul iple unc ionaliza ion o he b omina ed posi ions ia he Suzuki–Miyau a c oss-coupling eac ion in 3a (Table S1). The eac ion condi ions used in en y 1 and 2 we e epo ed in he li e a u e o he mul iple unc ionaliza ion o BODIPYs [34,35]. Fo en y 1, he eac ion was incomple e, and mul iple p oduc s we e obse ed, while o en y 2, he desi ed p oduc 4 was isola ed in 42% yield. When we used Pd(OAc)2 and SPhos, along wi h K3PO4 as a base, he yield o 4 inc eased o 52% (en y 3 in Table S1). Once he bes condi ions we e de e mined, we se ou o eac 3a–e wi h se e al (he )a ylbo onic acids o di e en elec onic na u es o s udy he scope o he Suzuki– Miyau a c oss-coupling eac ion. The esul s ob ained o he mul iple unc ionaliza ion o 3a–e a e shown in Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ions ook place smoo hly and ga e he poly (he )a yla ed p oduc s in modes o good yields (41 o 83%) in ela i ely sho eac ion imes. In gene al, elec on- ich bo onic acids ga e he highes yields (en ies 1–4, 9 and 11 in Table 1) and sho es eac ion imes. Speci ically, he bes esul s, bo h in yield (65 o 83%) and eac ion imes, we e ob ained using 2- hienylbo onic acid, since he eac ions ook only 20 min. While he elec on-poo bo onic acids equi ed longe eac ion imes (en ies 10 and 12 in Table 1). No clea end was obse ed when he meso-a yl subs i uen s we e modi ied. Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ion on 3a–e 1. En y A R-B(OH)2 Reac ion Time Yield 2 (%) Compound 1 S 20 min 80 4a 2 S 20 min 83 4b 3 S 20 min 65 4c 4 MeO S 25 min 76 4d 5 OHC S 2 h 55 4e 6 4 h 52 4 7 4 h 57 4g 8 F 3 C 5 h 41 4h 9 MeO 2 h 65 4i 10 MeOC 14 h 65 4j 11 MeO Me 3 Si 4 h 63 4k 12 MeO NC 16 h 57 4l 1 Condi ions: 3a (1 equi .), bo onic acid (8 equi .) Pd(OAc)2 (10 mol%), SPhos (22 mol%), K3PO4 (16 equi .) in PhCH3 a 90 °C oo no e. 2 Isola ed yield. 2.2. Pho ophysical P ope ies The a yla ion o he py oles ex ends he ch omopho ic delocalized π-sys em pushing he spec al bands owa ds he ed edge o he isible (abso p ion and emission o 4 and 4g placed a a ound 590 and 620 nm, espec i ely, Figu e 1). The meso-phenyl does no ake pa in he delocalized amewo k o he dipy in owing o i s wis ed geome ical a angemen ( heo e ically p edic ed o sion angle a ound 70° om g ound Molecules 2023, 28, x FOR PEER REVIEW 4 o 15 Nex , he key s ep o ou syn he ic plan was conduc ed, ha is, he mul iple unc ionaliza ion o he b omina ed posi ions ia he Suzuki–Miyau a c oss-coupling eac ion in 3a (Table S1). The eac ion condi ions used in en y 1 and 2 we e epo ed in he li e a u e o he mul iple unc ionaliza ion o BODIPYs [34,35]. Fo en y 1, he eac ion was incomple e, and mul iple p oduc s we e obse ed, while o en y 2, he desi ed p oduc 4 was isola ed in 42% yield. When we used Pd(OAc)2 and SPhos, along wi h K3PO4 as a base, he yield o 4 inc eased o 52% (en y 3 in Table S1). Once he bes condi ions we e de e mined, we se ou o eac 3a–e wi h se e al (he )a ylbo onic acids o di e en elec onic na u es o s udy he scope o he Suzuki– Miyau a c oss-coupling eac ion. The esul s ob ained o he mul iple unc ionaliza ion o 3a–e a e shown in Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ions ook place smoo hly and ga e he poly (he )a yla ed p oduc s in modes o good yields (41 o 83%) in ela i ely sho eac ion imes. In gene al, elec on- ich bo onic acids ga e he highes yields (en ies 1–4, 9 and 11 in Table 1) and sho es eac ion imes. Speci ically, he bes esul s, bo h in yield (65 o 83%) and eac ion imes, we e ob ained using 2- hienylbo onic acid, since he eac ions ook only 20 min. While he elec on-poo bo onic acids equi ed longe eac ion imes (en ies 10 and 12 in Table 1). No clea end was obse ed when he meso-a yl subs i uen s we e modi ied. Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ion on 3a–e 1. En y A R-B(OH)2 Reac ion Time Yield 2 (%) Compound 1 S 20 min 80 4a 2 S 20 min 83 4b 3 S 20 min 65 4c 4 MeO S 25 min 76 4d 5 OHC S 2 h 55 4e 6 4 h 52 4 7 4 h 57 4g 8 F 3 C 5 h 41 4h 9 MeO 2 h 65 4i 10 MeOC 14 h 65 4j 11 MeO Me 3 Si 4 h 63 4k 12 MeO NC 16 h 57 4l 1 Condi ions: 3a (1 equi .), bo onic acid (8 equi .) Pd(OAc)2 (10 mol%), SPhos (22 mol%), K3PO4 (16 equi .) in PhCH3 a 90 °C oo no e. 2 Isola ed yield. 2.2. Pho ophysical P ope ies The a yla ion o he py oles ex ends he ch omopho ic delocalized π-sys em pushing he spec al bands owa ds he ed edge o he isible (abso p ion and emission o 4 and 4g placed a a ound 590 and 620 nm, espec i ely, Figu e 1). The meso-phenyl does no ake pa in he delocalized amewo k o he dipy in owing o i s wis ed geome ical a angemen ( heo e ically p edic ed o sion angle a ound 70° om g ound 4 h 63 4k 12 Molecules 2023, 28, x FOR PEER REVIEW 4 o 15 Nex , he key s ep o ou syn he ic plan was conduc ed, ha is, he mul iple unc ionaliza ion o he b omina ed posi ions ia he Suzuki–Miyau a c oss-coupling eac ion in 3a (Table S1). The eac ion condi ions used in en y 1 and 2 we e epo ed in he li e a u e o he mul iple unc ionaliza ion o BODIPYs [34,35]. Fo en y 1, he eac ion was incomple e, and mul iple p oduc s we e obse ed, while o en y 2, he desi ed p oduc 4 was isola ed in 42% yield. When we used Pd(OAc)2 and SPhos, along wi h K3PO4 as a base, he yield o 4 inc eased o 52% (en y 3 in Table S1). Once he bes condi ions we e de e mined, we se ou o eac 3a–e wi h se e al (he )a ylbo onic acids o di e en elec onic na u es o s udy he scope o he Suzuki– Miyau a c oss-coupling eac ion. The esul s ob ained o he mul iple unc ionaliza ion o 3a–e a e shown in Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ions ook place smoo hly and ga e he poly (he )a yla ed p oduc s in modes o good yields (41 o 83%) in ela i ely sho eac ion imes. In gene al, elec on- ich bo onic acids ga e he highes yields (en ies 1–4, 9 and 11 in Table 1) and sho es eac ion imes. Speci ically, he bes esul s, bo h in yield (65 o 83%) and eac ion imes, we e ob ained using 2- hienylbo onic acid, since he eac ions ook only 20 min. While he elec on-poo bo onic acids equi ed longe eac ion imes (en ies 10 and 12 in Table 1). No clea end was obse ed when he meso-a yl subs i uen s we e modi ied. Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ion on 3a–e 1. En y A R-B(OH)2 Reac ion Time Yield 2 (%) Compound 1 S 20 min 80 4a 2 S 20 min 83 4b 3 S 20 min 65 4c 4 MeO S 25 min 76 4d 5 OHC S 2 h 55 4e 6 4 h 52 4 7 4 h 57 4g 8 F 3 C 5 h 41 4h 9 MeO 2 h 65 4i 10 MeOC 14 h 65 4j 11 MeO Me 3 Si 4 h 63 4k 12 MeO NC 16 h 57 4l 1 Condi ions: 3a (1 equi .), bo onic acid (8 equi .) Pd(OAc)2 (10 mol%), SPhos (22 mol%), K3PO4 (16 equi .) in PhCH3 a 90 °C oo no e. 2 Isola ed yield. 2.2. Pho ophysical P ope ies The a yla ion o he py oles ex ends he ch omopho ic delocalized π-sys em pushing he spec al bands owa ds he ed edge o he isible (abso p ion and emission o 4 and 4g placed a a ound 590 and 620 nm, espec i ely, Figu e 1). The meso-phenyl does no ake pa in he delocalized amewo k o he dipy in owing o i s wis ed geome ical a angemen ( heo e ically p edic ed o sion angle a ound 70° om g ound Molecules 2023, 28, x FOR PEER REVIEW 4 o 15 Nex , he key s ep o ou syn he ic plan was conduc ed, ha is, he mul iple unc ionaliza ion o he b omina ed posi ions ia he Suzuki–Miyau a c oss-coupling eac ion in 3a (Table S1). The eac ion condi ions used in en y 1 and 2 we e epo ed in he li e a u e o he mul iple unc ionaliza ion o BODIPYs [34,35]. Fo en y 1, he eac ion was incomple e, and mul iple p oduc s we e obse ed, while o en y 2, he desi ed p oduc 4 was isola ed in 42% yield. When we used Pd(OAc)2 and SPhos, along wi h K3PO4 as a base, he yield o 4 inc eased o 52% (en y 3 in Table S1). Once he bes condi ions we e de e mined, we se ou o eac 3a–e wi h se e al (he )a ylbo onic acids o di e en elec onic na u es o s udy he scope o he Suzuki– Miyau a c oss-coupling eac ion. The esul s ob ained o he mul iple unc ionaliza ion o 3a–e a e shown in Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ions ook place smoo hly and ga e he poly (he )a yla ed p oduc s in modes o good yields (41 o 83%) in ela i ely sho eac ion imes. In gene al, elec on- ich bo onic acids ga e he highes yields (en ies 1–4, 9 and 11 in Table 1) and sho es eac ion imes. Speci ically, he bes esul s, bo h in yield (65 o 83%) and eac ion imes, we e ob ained using 2- hienylbo onic acid, since he eac ions ook only 20 min. While he elec on-poo bo onic acids equi ed longe eac ion imes (en ies 10 and 12 in Table 1). No clea end was obse ed when he meso-a yl subs i uen s we e modi ied. Table 1. Mul iple Suzuki–Miyau a c oss-coupling eac ion on 3a–e 1. En y A R-B(OH)2 Reac ion Time Yield 2 (%) Compound 1 S 20 min 80 4a 2 S 20 min 83 4b 3 S 20 min 65 4c 4 MeO S 25 min 76 4d 5 OHC S 2 h 55 4e 6 4 h 52 4 7 4 h 57 4g 8 F 3 C 5 h 41 4h 9 MeO 2 h 65 4i 10 MeOC 14 h 65 4j 11 MeO Me 3 Si 4 h 63 4k 12 MeO NC 16 h 57 4l 1 Condi ions: 3a (1 equi .), bo onic acid (8 equi .) Pd(OAc)2 (10 mol%), SPhos (22 mol%), K3PO4 (16 equi .) in PhCH3 a 90 °C oo no e. 2 Isola ed yield. 2.2. Pho ophysical P ope ies The a yla ion o he py oles ex ends he ch omopho ic delocalized π-sys em pushing he spec al bands owa ds he ed edge o he isible (abso p ion and emission o 4 and 4g placed a a ound 590 and 620 nm, espec i ely, Figu e 1). The meso-phenyl does no ake pa in he delocalized amewo k o he dipy in owing o i s wis ed geome ical a angemen ( heo e ically p edic ed o sion angle a ound 70° om g ound 16 h 57 4l 1 Condi ions: 3a (1 equi .), bo onic acid (8 equi .) Pd(OAc) 2 (10 mol%), SPhos (22 mol%), K 3 PO 4 (16 equi .) in PhCH3a 90 ◦C oo no e. 2Isola ed yield. 2.2. Pho ophysical P ope ies The a yla ion o he py oles ex ends he ch omopho ic delocalized π -sys em pushing he spec al bands owa ds he ed edge o he isible (abso p ion and emission o 4 and 4g placed a a ound 590 and 620 nm, espec i ely, Figu e 1). The meso-phenyl does no Molecules 2023,28, 4750 5 o 15 ake pa in he delocalized amewo k o he dipy in owing o i s wis ed geome ical a angemen ( heo e ically p edic ed o sion angle a ound 70 ◦ om g ound s a e op imized geome ies) imposed by s e ic easons. The a ained luo escence e iciencies a e lowe (a ound 30%, Table 2) han hose usually epo ed o g een–yellow emi ing BODIPYs (usually highe han 80%). This end is ela ed o he ee mo ion o he pe iphe al phenyls, which enhances he non- adia i e elaxa ion channels ela ed wi h con o ma ional eedom (no e he unusually high S okes shi , a ound 1000 cm −1 , sugges ing geome ic elaxa ion upon exci a ion). Wi h his line o easoning, p e ious publica ions dealing wi h hep aphenyla ed BODIPYs epo ed simila alues o luo escence e iciencies and pinpoin ed in e nal con e sion as he main eason [36]. Molecules 2023, 28, x FOR PEER REVIEW 5 o 15 s a e op imized geome ies) imposed by s e ic easons. The a ained luo escence e iciencies a e lowe (a ound 30%, Table 2) han hose usually epo ed o g een–yellow emi ing BODIPYs (usually highe han 80%). This end is ela ed o he ee mo ion o he pe iphe al phenyls, which enhances he non- adia i e elaxa ion channels ela ed wi h con o ma ional eedom (no e he unusually high S okes shi , a ound 1000 cm−1, sugges ing geome ic elaxa ion upon exci a ion). Wi h his line o easoning, p e ious publica ions dealing wi h hep aphenyla ed BODIPYs epo ed simila alues o luo escence e iciencies and pinpoin ed in e nal con e sion as he main eason [36]. Figu e 1. Rep esen a i e abso p ion (o ange) and luo escence ( ed) spec a o he polyphenylBODIPY 4 (see Figu e S1 o he spec a o he es o dyes o his amily) in dilu ed solu ions o cyclohexane. The co esponding con ou maps o he on ie o bi als a e also enclosed. Table 2. Pho ophysical (2 μM) and lase (0.5–0.75 mM) p ope ies o he polyphenylBODIPYs in e hyl ace a e. Full pho ophysical and lase da a in mo e media a e lis ed in Tables S2 and S3, espec i ely. Dye λ ab 1 (nm) ε max ∙10 −4 2 (M −1 ∙cm −1 ) λ l 3 (nm) ф 4 τ 5 (ns) λ la 6 (nm) %E 7 E dose 8 (GJ/mol) 4 577.0 5.0 623.0 0.26 2.28 630.0 8.5 9.0 4g 579.0 5.1 618.0 0.32 2.92 628.0 9.8 9.4 4h 566.5 7.0 597.5 0.47 3.50 611.0 13.5 14.1 4i 615.0 3.9 653.0 0.78 4.12 670.0 6.4 5.9 4j 585.0 6.1 622.0 0.52 3.72 636.0 8.3 13.5 4k 584.5 4.0 617.0 0.83 5.37 625.0 17.8 2.3 4l 569.0 6.8 604.0 0.53 4.22 612.0 11.2 5.2 1 Abso p ion wa eleng h. 2 Mola abso p ion. 3 Fluo escence wa eleng h. 4 Fluo escence quan um yield. 5 Fluo escence li e ime. 6 Lasing wa eleng h. 7 Lase e iciency. 8 Pho os abili y, de ined as he amoun o pumping ene gy abso bed by he dye o e ain 90% o he lase induced emission. In his ega d, he deco a ion o he a yls g a ed on he ch omopho ic py oles wi h elec on wi hd awing o elec on eleasing moie ies a he pa a-posi ion is a sui able app oach o amelio a e he luo escen esponse (Table 2 and Figu e 2). The a achmen o elec on accep o g oups does no al e he spec al band posi ions, bu p og essi ely enhances he luo escence e iciency, being wice ha o he o me ones o he dyes bea ing ca bonyl (4j, Hamme pa ame e σp+ = 0.55) and i luo ome hyl (4h, σp+ = 0.61), and e en eaching an e iciency o up o 75% o he dye bea ing cyano (4l, σp+ = 0.66), he s onges elec on wi hd awing uni among he ones es ed so a (Figu e 2). I is wo h men ioning ha he coexis ence o his las g oup wi h pa a-me hoxy in he 8-phenyl Figu e 1. Rep esen a i e abso p ion (o ange) and luo escence ( ed) spec a o he polyphenylBODIPY 4 (see Figu e S1 o he spec a o he es o dyes o his amily) in dilu ed solu ions o cyclohexane. The co esponding con ou maps o he on ie o bi als a e also enclosed. Table 2. Pho ophysical (2 µ M) and lase (0.5–0.75 mM) p ope ies o he polyphenylBODIPYs in e hyl ace a e. Full pho ophysical and lase da a in mo e media a e lis ed in Tables S2 and S3, espec i ely. Dye λab 1 (nm) εmax·10−4 2 (M−1·cm−1) λ l3 (nm) φ4τ5 (ns) λla 6 (nm) %E 7Edose 8 (GJ/mol) 4 577.0 5.0 623.0 0.26 2.28 630.0 8.5 9.0 4g 579.0 5.1 618.0 0.32 2.92 628.0 9.8 9.4 4h 566.5 7.0 597.5 0.47 3.50 611.0 13.5 14.1 4i 615.0 3.9 653.0 0.78 4.12 670.0 6.4 5.9 4j 585.0 6.1 622.0 0.52 3.72 636.0 8.3 13.5 4k 584.5 4.0 617.0 0.83 5.37 625.0 17.8 2.3 4l 569.0 6.8 604.0 0.53 4.22 612.0 11.2 5.2 1 Abso p ion wa eleng h. 2 Mola abso p ion. 3 Fluo escence wa eleng h. 4 Fluo escence quan um yield. 5 Fluo escence li e ime. 6 Lasing wa eleng h. 7 Lase e iciency. 8 Pho os abili y, de ined as he amoun o pumping ene gy abso bed by he dye o e ain 90% o he lase induced emission. In his ega d, he deco a ion o he a yls g a ed on he ch omopho ic py oles wi h elec on wi hd awing o elec on eleasing moie ies a he pa a-posi ion is a sui able app oach o amelio a e he luo escen esponse (Table 2and Figu e 2). The a achmen o elec on accep o g oups does no al e he spec al band posi ions, bu p og essi ely enhances he luo escence e iciency, being wice ha o he o me ones o he dyes bea ing ca bonyl ( 4j , Hamme pa ame e σp+ = 0.55) and i luo ome hyl ( 4h , σp+ = 0.61), and e en eaching an e iciency o up o 75% o he dye bea ing cyano ( 4l , σp+ = 0.66), he s onges elec on wi hd awing uni among he ones es ed so a (Figu e 2). I is wo h men ioning Molecules 2023,28, 4750 6 o 15 ha he coexis ence o his las g oup wi h pa a-me hoxy in he 8-phenyl inc eases he cha ge sepa a ion, explaining he sensi i i y o he luo escen esponse o 4l wi h he sol en pola i y (down o 48% in ace oni ile, Figu e 2). Molecules 2023, 28, x FOR PEER REVIEW 6 o 15 inc eases he cha ge sepa a ion, explaining he sensi i i y o he luo escen esponse o 4l wi h he sol en pola i y (down o 48% in ace oni ile, Figu e 2). Figu e 2. E olu ion o he luo escen e iciency in media o di e en pola i y o ep esen a i e polyphenylBODIPYs bea ing elec on accep o o elec on dono moie ies a he pa a posi ion o he pe iphe al py olic phenyls. I is likely ha his unc ionaliza ion o he a yls wi h elec on ich g oups enhances he delocaliza ion be ween he dipy in and he phenyls, leading o less single bond cha ac e in he linkage and he eby dec easing he ee mo ion o he pe iphe al ings. In ac , heo e ically op imized geome ies a he g ound s a e e eal ha bo h he wis ing angle and he bond leng h connec ing he phenyls and he py oles, dec ease as he a yls a e pa a- unc ionalized (a e age alues om 45° o 35° and om 1.45 Å o 1.40 Å, espec i ely). Fu he e idence o he success o his s a egy o educe in e nal con e sion is p o ided by 4i and 4k (Figu e 2). E en he sole p esence o he elec onically neu al ime hylsilane (4i, σp+ = 0.02) yields a ema kable inc ease in he luo escence ha app oaches 90%. Mo eo e , he elec on dono me hoxy (4k, σp+ = −0.78) induces a u he ba hoch omic shi and ende s no able luo escence e iciencies eaching almos 100% (Figu e 2). Howe e , in his case, he ou elec on dono uni s deco a ing he elec on de icien bo on–dipy in co e we e able o induce cha ge sepa a ion, as sugges ed by he sol en pola i y igge ed dec ease in he luo escence ou pu (Figu e 2), and he unexpec ed posi i e sol a och omism o he luo escence band, opposi e o he nega i e sol a och omism egis e ed o he abso p ion band (Table S2). The e o e, pa a- unc ionaliza ion o he phenyls deco a ing he ch omopho ic py oles is a good s a egy o enhance he luo escence signal o poliphenylBODIPYs. To u he push he spec al bands and each he a - ed–NIR egion he py olic phenyls we e eplaced by hiophene, ea u ing highe elec on eleasing abili y (σp+ = −0.43). In ac , he abso p ion band o he poly hiopheneBODIPYs is placed a a ound 630– 650 nm, depending on he meso-phenyl subs i u ion (Table 3). Thus, he highes ba hoch omic shi is achie ed upon o myla ion o he 8-phenyl (4e), since elec on wi hd awing g oups a he meso posi ion u he s abilize he LUMO owing o i s high elec onic densi y loca ed a he ch omopho ic posi ion (Figu e 1). Acco dingly, he luo escence band is placed a ound 680–710 nm, being again he o myla ed dye 4e, he one displaying he eddes emission (Figu e 3). Ne e heless, an inc ease in he sol en pola i y ma kedly a ec ed he luo escence signa u es o his se o poly hiopheneBODIPYs. O e all, he luo escence e iciency was lowe (a ound 15 o 20%, wi h he excep ion o 4d, which eached almos 40%), han o he polya yla ed Figu e 2. E olu ion o he luo escen e iciency in media o di e en pola i y o ep esen a i e polyphenylBODIPYs bea ing elec on accep o o elec on dono moie ies a he pa a posi ion o he pe iphe al py olic phenyls. I is likely ha his unc ionaliza ion o he a yls wi h elec on ich g oups enhances he delocaliza ion be ween he dipy in and he phenyls, leading o less single bond cha ac- e in he linkage and he eby dec easing he ee mo ion o he pe iphe al ings. In ac , heo e ically op imized geome ies a he g ound s a e e eal ha bo h he wis ing angle and he bond leng h connec ing he phenyls and he py oles, dec ease as he a yls a e pa a- unc ionalized (a e age alues om 45 ◦ o 35 ◦ and om 1.45 Å o 1.40 Å, espec i ely). Fu he e idence o he success o his s a egy o educe in e nal con e sion is p o ided by 4i and 4k (Figu e 2). E en he sole p esence o he elec onically neu al ime hylsilane ( 4i , σp+ = 0.02) yields a ema kable inc ease in he luo escence ha app oaches 90%. Mo eo e , he elec on dono me hoxy ( 4k , σp+ = − 0.78) induces a u he ba hoch omic shi and en- de s no able luo escence e iciencies eaching almos 100% (Figu e 2). Howe e , in his case, he ou elec on dono uni s deco a ing he elec on de icien bo on–dipy in co e we e able o induce cha ge sepa a ion, as sugges ed by he sol en pola i y igge ed dec ease in he luo escence ou pu (Figu e 2), and he unexpec ed posi i e sol a och omism o he luo- escence band, opposi e o he nega i e sol a och omism egis e ed o he abso p ion band (Table S2). The e o e, pa a- unc ionaliza ion o he phenyls deco a ing he ch omopho ic py oles is a good s a egy o enhance he luo escence signal o poliphenylBODIPYs. To u he push he spec al bands and each he a - ed–NIR egion he py olic phenyls we e eplaced by hiophene, ea u ing highe elec on eleasing abili y (σp+=−0.43) . In ac , he abso p ion band o he poly hiopheneBODIPYs is placed a a ound 630–650 nm, depending on he meso-phenyl subs i u ion (Table 3). Thus, he highes ba hoch omic shi is achie ed upon o myla ion o he 8-phenyl ( 4e ), since elec on wi hd awing g oups a he meso posi ion u he s abilize he LUMO owing o i s high elec onic densi y loca ed a he ch omopho ic posi ion (Figu e 1). Acco dingly, he luo escence band is placed a ound 680–710 nm, being again he o myla ed dye 4e , he one displaying he eddes emission (Figu e 3). Ne e heless, an inc ease in he sol en pola i y ma kedly a ec ed he luo escence signa u es o his se o poly hiopheneBODIPYs. O e all, he luo escence e iciency was lowe (a ound 15 o 20%, wi h he excep ion o 4d , which eached almos 40%), han o he polya yla ed analogues in apola media. An inc ease in he sol en Molecules 2023,28, 4750 7 o 15 pola i y implies a p onounced quenching o he emission, as e lec ed in he low e iciencies (down o 2%) and as li e imes (hund eds o picoseconds) eco ded (Table 3 s. Table 2). Mo eo e , he luo escen band displays a ma ked ba hoch omic shi (a ound 30 nm) wi h he sol en pola i y (Table 3and Figu e 3). Such an en i onmen s abilizes he cha ge sepa a ion and a da k cha ge sepa a ed s a e (CS) can be popula ed. Thus, 4e showing push–pull ea u es, emi s a 735 nm in pola media (Figu e 3), he eddes emission he ein eco ded, bu wi h low luo escence (jus 2%, Table 3). The e o e, he elec on eleasing abili y o he hiophenes is able o induce cha ge ans e (CT) cha ac e o he emi ing s a e, becoming a s a e o high pola i y. Table 3. Pho ophysical (2 µ M) p ope ies, in sol en s o di e en pola i y; cyclohexane (c-hex), e hyl ace a e (E OAc) and ace oni ile (ACN), and lase (0.5–0.75 mM) p ope ies in e hyl ace a e o he poly hiopheneBODIPYs. Full pho ophysical and lase da a in mo e media a e lis ed in Tables S4 and S5, espec i ely. Dye Sol en λab 1 (nm) εmax·10−4 2 (M−1·cm−1) λ l3 (nm) φ4τ5 (ns) λla 6 (nm) %E 7Edose 8 (GJ/mol) c-hex 638.5 6.0 688.0 0.16 3.47 4a E OAc 630.0 5.0 700.5 0.08 1.07 717.0 11.8 1.3 ACN 624.5 4.1 711.5 0.03 0.42 c-hex 636.0 4.0 682.0 0.20 3.83 4b E OAc 628.0 3.4 695.0 0.09 1.23 712.0 11.4 6.0 ACN 621.5 3.0 707.0 0.03 0.50 c-hex 639.0 5.3 685.5 0.21 3.85 4c E OAc 632.5 4.6 696.0 0.11 1.32 710.0 9.3 7.6 ACN 627.0 4.1 705.5 0.04 0.55 c-hex 629.0 6.5 678.5 0.39 4.10 4d E OAc 625.0 5.1 690.0 0.15 1.41 705.0 20.5 10.0 ACN 619.0 4.2 703.5 0.05 0.62 c-hex 650.0 4.8 708.0 0.17 1.65 4e E OAc 639.0 4.1 721.0 0.04 0.41 744.0 8.7 7.6 ACN 634.5 3.3 736.0 0.02 0.41 1 Abso p ion wa eleng h. 2 Mola abso p ion. 3 Fluo escen wa eleng h. 4 Fluo escence quan um yield. 5 Fluo es- cence li e ime. 6 Lasing wa eleng h. 7 Lase e iciency. 8 Pho os abili y, de ined as he amoun o pumping ene gy abso bed by he dye o e ain 90% o he lase induced emission. Molecules 2023, 28, x FOR PEER REVIEW 7 o 15 analogues in apola media. An inc ease in he sol en pola i y implies a p onounced quenching o he emission, as e lec ed in he low e iciencies (down o 2%) and as li e imes (hund eds o picoseconds) eco ded (Table 3 s. Table 2). Mo eo e , he luo escen band displays a ma ked ba hoch omic shi (a ound 30 nm) wi h he sol en pola i y (Table 3 and Figu e 3). Such an en i onmen s abilizes he cha ge sepa a ion and a da k cha ge sepa a ed s a e (CS) can be popula ed. Thus, 4e showing push–pull ea u es, emi s a 735 nm in pola media (Figu e 3), he eddes emission he ein eco ded, bu wi h low luo escence (jus 2%, Table 3). The e o e, he elec on eleasing abili y o he hiophenes is able o induce cha ge ans e (CT) cha ac e o he emi ing s a e, becoming a s a e o high pola i y. Figu e 3. No malized abso p ion and luo escence (shadow illed) spec a o 4e as a ep esen a i e dye o he poly hiopheneBODIPYs (see Figu e S2 o he spec a o he es o dyes o his amily) in dilu ed solu ions. Table 3. Pho ophysical (2 μM) p ope ies, in sol en s o di e en pola i y; cyclohexane (c-hex), e hyl ace a e (E OAc) and ace oni ile (ACN), and lase (0.5–0.75 mM) p ope ies in e hyl ace a e o he poly hiopheneBODIPYs. Full pho ophysical and lase da a in mo e media a e lis ed in Table S4 and S5, espec i ely. Dye Sol en λ ab 1 (nm) ε max ∙10 −4 2 (M −1 ∙cm −1 ) λ l 3 (nm) ф 4 τ 5 (ns) λ la 6 (nm) %E 7 E dose 8 (GJ/mol) c-hex 638.5 6.0 688.0 0.16 3.47 4a E OAc 630.0 5.0 700.5 0.08 1.07 717.0 11.8 1.3 ACN 624.5 4.1 711.5 0.03 0.42 c-hex 636.0 4.0 682.0 0.20 3.83 4b E OAc 628.0 3.4 695.0 0.09 1.23 712.0 11.4 6.0 ACN 621.5 3.0 707.0 0.03 0.50 c-hex 639.0 5.3 685.5 0.21 3.85 4c E OAc 632.5 4.6 696.0 0.11 1.32 710.0 9.3 7.6 ACN 627.0 4.1 705.5 0.04 0.55 c-hex 629.0 6.5 678.5 0.39 4.10 4d E OAc 625.0 5.1 690.0 0.15 1.41 705.0 20.5 10.0 ACN 619.0 4.2 703.5 0.05 0.62 c-hex 650.0 4.8 708.0 0.17 1.65 4e E OAc 639.0 4.1 721.0 0.04 0.41 744.0 8.7 7.6 ACN 634.5 3.3 736.0 0.02 0.41 1 Abso p ion wa eleng h. 2 Mola abso p ion. 3 Fluo escen wa eleng h. 4 Fluo escence quan um yield. 5 Fluo escence li e ime. 6 Lasing wa eleng h. 7 Lase e iciency. 8 Pho os abili y, de ined as he amoun o pumping ene gy abso bed by he dye o e ain 90% o he lase induced emission. Figu e 3. No malized abso p ion and luo escence (shadow illed) spec a o 4e as a ep esen a i e dye o he poly hiopheneBODIPYs (see Figu e S2 o he spec a o he es o dyes o his amily) in dilu ed solu ions. Molecules 2023,28, 4750 8 o 15 Such a ea u e can be en isaged om Figu e 4. The g a ing o elec on ich hiophene leads o a mo e ex ended π -sys em, sus ained by he simula ed HOMO con ou map, whe e he π -elec onic densi y is clea ly spanned o e he whole molecule, comp ising bo h BODIPY and hiophenes. Howe e , he exci a ion implies a ma ked elec onic ans e om he hiophenes o he BODIPY co e, as suppo ed by he heo e ically p edic ed LUMO, which is mainly loca ed a he la e moie y. Fu he mo e, upon o myla ion o he 8-phenyl, he shi o he elec onic densi y owa ds he BODIPY is mo e p onounced, eaching he 8- o myla ed ing, owing o he elec on wi hd awing e ec o his unc ionaliza ion. Thus, his elec onic ea angemen upon exci a ion an icipa es he CT cha ac e o he emi ing s a e, s eng hened in 4e . The e o e, poly hiopheneBODIPYs enable us o push he emission deepe in o he a - ed–NIR egion (beyond 700 nm), bu in u n he e iciency dec eases, owing o he lowe ene gy gap and he sol en exe ed s abiliza ion o cha ge sepa a ion. Molecules 2023, 28, x FOR PEER REVIEW 8 o 15 Such a ea u e can be en isaged om Figu e 4. The g a ing o elec on ich hiophene leads o a mo e ex ended π-sys em, sus ained by he simula ed HOMO con ou map, whe e he π-elec onic densi y is clea ly spanned o e he whole molecule, comp ising bo h BODIPY and hiophenes. Howe e , he exci a ion implies a ma ked elec onic ans e om he hiophenes o he BODIPY co e, as suppo ed by he heo e ically p edic ed LUMO, which is mainly loca ed a he la e moie y. Fu he mo e, upon o myla ion o he 8-phenyl, he shi o he elec onic densi y owa ds he BODIPY is mo e p onounced, eaching he 8- o myla ed ing, owing o he elec on wi hd awing e ec o his unc ionaliza ion. Thus, his elec onic ea angemen upon exci a ion an icipa es he CT cha ac e o he emi ing s a e, s eng hened in 4e. The e o e, poly hiopheneBODIPYs enable us o push he emission deepe in o he a - ed–NIR egion (beyond 700 nm), bu in u n he e iciency dec eases, owing o he lowe ene gy gap and he sol en exe ed s abiliza ion o cha ge sepa a ion. Figu e 4. Con ou maps o he on ie molecula o bi als calcula ed om op imized g ound s a e geome ies (wb97xd/6-311 + g*) o ep esen a i e polyphenylBODIPY 4 , and poly hiopheneBODIPYs 4b and 4e. The co esponding heo e ically p edic ed abso p ion spec a ( d wb97xd) a e also depic ed. Mo i a ed by he ongoing CT upon a achmen o hiophene, we es ed he iabili y o hese poly hiopheneBODIPYs as halogen- ee single oxygen pho osensi ize s. One o he mos cu en ly ac i e in pho odynamic he apy is he p omo ion o CT as an in e media e o each he a ge iple s a e, which enables single oxygen gene a ion [37]. In ac , hiophene- used BODIPYs we e epo ed o pho osensi ize single oxygen h ough ICT-media ed in e sys em c ossing [38,39]. Howe e , in he he ein epo ed BODIPYs bea ing di ec ly linked iophenes, no single oxygen emission was de ec ed, nei he unde d as ic condi ions (dye concen a ion, exci a ion sou ces) no in di e en sol en s whe e he single oxygen li e ime is longe ( oluene, chlo o o m). I is no ewo hy ha he iple s a e popula ion om a CT implies a sub le balance be ween CS and cha ge ecombina ion (CR). In o he wo ds, enough CS should be p omo ed o s abilize he CT s a e, bu a he same ime, he CR p obabili y should be high enough o a e wa ds popula e he iple s a e [40]. In he BODIPYs desc ibed he e, such es ained balance is displaced o CS owing o he simul aneous p esence o ou elec on dono pe iphe al hiophenes. Thus, he iple s a e is no eached om he CT and he exci a ion ene gy is dissipa ed h ough Figu e 4. Con ou maps o he on ie molecula o bi als calcula ed om op imized g ound s a e geome ies (wb97xd/6-311 + g*) o ep esen a i e polyphenylBODIPY 4 , and poly hiopheneBOD- IPYs 4b and 4e . The co esponding heo e ically p edic ed abso p ion spec a ( d wb97xd) a e also depic ed. Mo i a ed by he ongoing CT upon a achmen o hiophene, we es ed he iabili y o hese poly hiopheneBODIPYs as halogen- ee single oxygen pho osensi ize s. One o he mos cu en ly ac i e in pho odynamic he apy is he p omo ion o CT as an in e media e o each he a ge iple s a e, which enables single oxygen gene a ion [ 37 ]. In ac , hiophene- used BODIPYs we e epo ed o pho osensi ize single oxygen h ough ICT- media ed in e sys em c ossing [38,39]. Howe e , in he he ein epo ed BODIPYs bea ing di ec ly linked iophenes, no single oxygen emission was de ec ed, nei he unde d as ic condi ions (dye concen a ion, exci a ion sou ces) no in di e en sol en s whe e he single oxygen li e ime is longe ( oluene, chlo o o m). I is no ewo hy ha he iple s a e popula ion om a CT implies a sub le balance be ween CS and cha ge ecombina ion (CR). In o he wo ds, enough CS should be p omo ed o s abilize he CT s a e, bu a he same ime, he CR p obabili y should be high enough o a e wa ds popula e he iple s a e [ 40 ]. In he BODIPYs desc ibed he e, such es ained balance is displaced o CS owing o he simul aneous p esence o ou elec on dono pe iphe al hiophenes. Thus, he iple s a e is no eached om he CT and he exci a ion ene gy is dissipa ed h ough non- adia i e unnels, leading o luo escence quenching and no single oxygen gene a ion. Molecules 2023,28, 4750 9 o 15 2.3. Lase P ope ies The absence o popula ion o he iple mani old p omp ed us o es hese ex ended BODIPYs as pho oac i e media o unable o ganic lase s. All o hem show he ypical b oad dye lase emission ( ull wid h a hal maximum, FWHM, o e all a ound 5 nm) in he ed–NIR edge o he isible, anging om 600 nm o 760 nm (Figu e 5), a e being ans e sally pumped by a wa eleng h- unable Op ical Pa ame ic Oscilla o (OPO), which allows i adia ion o each dye a i s maximum abso p ion wa eleng h (see Sec ion 3 o de ails). The concen a ion ha op imizes he lase e iciency, unde s ood as he a io o he ou pu and inpu (pump) ene gies, depends on each dye (a ound 0.5–0.75 mM, Tables S3 and S5). In his sense, he lase ou pu e iciency inc eases wi h he concen a ion up o a maximum pla eau, om which i dec eases owing o eabso p ion/ eemission phenomena. The shi o he emission peak o longe wa eleng hs wi h he concen a ion inc ease backs up his in e p e a ion (Tables S3 and S5). In gene al e ms, he e olu ion o he lase wa eleng h co ela es well wi h he luo escen one (Tables 2and 3). Thus, wi hin he polya yla ed dyes, 4i , unc ionalized wi h me hoxy, shows he eddes lase emission ( om a ound 610–635 nm o 670 nm). Al e na i ely, he lase emission o he BODIPYs unc ionalized wi h hiophene is pushed deepe in o he ed (a ound 705–715 nm), mainly wi h he p esence o o myl in he 8-phenyl ( 4e , up o 745 nm), being he eddes one among all he es ed lase dyes. Molecules 2023, 28, x FOR PEER REVIEW 10 o 15 Figu e 5. Lase spec a scaled by he maximum e iciency o ep esen a i e polyphenylBODIPYs and poly hiopheneBODIPYs in e hyl ace a e o highligh he co e ed spec al window. Rega ding he pho os abili y, desc ibed as he equi ed ene gy o dec ease he lase induced luo escence (LIF) by 10% (see Sec ion 3 o de ails), ex emely high alues a e no expec ed owing o he con o ma ional eedom o he molecula s uc u e, which could enhance he dissipa ion o he pumping ene gy as hea . The i luo ome hyl (4h) is he mos sui ed unc ionaliza ion o enhance he s abili y agains i adia ion o polyphenylBODIPYs (Table 2). Indeed, his dye holds an op imal balance be ween lase e iciency (13.5%) and pho os abili y (14.1 GJ/mol). In his sense, i is no ewo hy ha he low pho os abili y o o he dyes is cha ac e ized by high emission e iciencies (4l and mainly 4i, bo h sha ing 8-anisole). I has been epo ed ha he 8-posi ion is in ol ed in he pho obleaching mechanism, and i s subs i u ion ( o ins ance wi h phenyl) is ecommended o enhance pho os abili y [42,43]. Howe e , i seems ha he pa a- unc ionaliza ion o his ing wi h he elec on dono me hoxy is de imen al in e ms o pho os abili y. Al e na i ely, he poly hiopheneBODIPYs show lowe pho os abili y, being in mos o hem a ound 6–7 GJ/mol and eaching 10 GJ/mol o 4d (Table 3). This dye is he one wi h he lowes non- adia i e deac i a ion a e cons an o he se ies (Table S4), which is also e lec ed in i s highe luo escence and lase e iciency (Table 3). In e es ingly, 4d dye bea s 8-anisole and he pho os abil y inc eases in con as o he end obse ed abo e wi h polyphenylBODIPYs (4i). This inding e eals ha i is challenging o es ablish gene al ules o unde s and he in e play be ween molecula s uc u e and pho os abili y. O he comme cial dyes lasing in his spec al egion, like he oxazine Nile Blue, main ain 90% o he lase ou pu a e endu ing 10 GJ/mol, simila o he he ein epo ed polyphenyl and poly hiopheneBODIPYs, which hence can be ca alogued as compe i i e b igh and long-las ing ac i e media o lase s. 3. Ma e ials and Me hods 3.1. Syn hesis De ails 1H and 13C NMR spec a we e eco ded on a B uke Ad ance III spec ome e (500 o 400 MHz) in deu e iochlo o o m (CDCl3) wi h ei he e ame hylsilane (TMS) (0.00 ppm 1H, 0.00 ppm 13C) o chlo o o m (7.26 ppm 1H, 77.00 ppm 13C) o as in e nal e e ence unless o he wise s a ed. Da a a e epo ed in he ollowing o de : chemical shi in pa s pe million (ppm), mul iplici ies (b (b oadened), s (single ), d (double ), ( iple ), q (qua e ), sex (sex e ), hex (hex e ), m (mul iple ), exch (exchangeable), and app (appa en )), coupling cons an s, J (Hz), and in eg a ion. In a ed spec a we e eco ded on a Pe kin-Elme -Spec um 100 FTIR spec opho ome e . Peaks a e epo ed (cm−1) wi h he ollowing ela i e in ensi ies: s (s ong, 67–100%), m (medium 40–65%), and w (weak 20– 39%). Mel ing poin s we e de e mined on a S an o d Resea ch Sys ems EZ-Mel appa a us Figu e 5. Lase spec a scaled by he maximum e iciency o ep esen a i e polyphenylBODIPYs and poly hiopheneBODIPYs in e hyl ace a e o highligh he co e ed spec al window. The polyphenyla ed dye 4 , shows a lase e iciency app oaching 10%, which is amelio- a ed upon pa a-subs i u ion o he py olic phenyls. Thus, he unc ionaliza ion wi h cyano ( 4l ), i luo ome hyl ( 4h ) and ime hylsilane ( 4k ) inc eases he lase ac ion (up o almos 18% o he la e , being almos wice ha o he e e ence dye 4 ), in good co ela ion wi h he obse ed inc ease in he luo escen esponse o hese dyes (Table 2). The excep ion o he ule is 4i , whe e in spi e o i s high luo escen e iciency, he lase e iciency dec eases. Likely, he cha ge ans e induced by he me hoxy g oups could accoun o his appa en misma ch. On he o he hand, he poly hiopheneBODIPYs show an unexpec edly high lase e iciency in iew o he eco ded low luo escence e iciencies (Table 3). Thus, hey show a mo e s uc u ed and b oade (FWHM up o 10 nm) band wi h an e iciency a ound 10%, eaching 20% o 4d , in line wi h he highe luo escence esponse eco ded o his dye. We should bea in mind ha his se o dyes a e cha ac e ized by la ge S okes shi s (a ound 1500 cm −1 , Table S4), which dec ease he eabso p ion/ eemission phenomena, and hence he losses in he esona o ca i y. Thei emi ing s a e is endowed wi h sub- s an ial CT cha ac e , leading o lowe luo escence e iciencies bu sho e li e imes (down o 1 ns). Such as decay seems o amelio a e he popula ion in e sion and enhance he s imula ed emission p obabili y, coun e balancing hei low p obabili y o spon aneous emission. Indeed, s y yl dyes (i.e., he comme cial LDS722), which a e also cha ac e ized