Theoretical design and study of Porous Carbon Nitride Fullerenes: A Novel Family of Cage Molecules

Theoretical design and study of Porous Carbon Nitride Fullerenes: a Novel Family of Cage Molecules Zacharias G. Fthenakis1, Nektarios Lathiotakis2 1Istituto Nanoscienze, Consiglio Nazionale delle Ricerche (CNR), and National Enterprise for nanoScience and nanoTechnology (NEST), Scuola Normale Superiore, Pisa, Italy 2 Theoretical and Physical Chemistry Institute, National Hellenic Research Foundation, Athens, Greece INTRODUCTION & AIM RESULTS CONCLUSION REFERENCES PCNF DESIGN •A novel family of cage molecules, the porous carbon nitride fullerenes (PCNFs) is proposed and studied thoretically.[1] •They are the 0-D counterparts of 2D graphitic carbon nitrides [2-6], in analogy with icosahedral fullerene, being the 0D counterpart of graphene. •We study two members of the PCNF family, the icosahedral C60N60 and C120N60. •We demonstrate their electronic, vibrational, and thermal stability. •Their revealed properties are promising for several applications. Question: Given that fullerenes are the 0D analogues of graphene (2D), do 0D analogues of 2D porous graphitic carbon nitrides exist? Conceptual design for PCNFs: •From large fullerenes of the form of Goldberg polyhedra by creating pores and replacing C with N atoms. •Using fullerenes and assuming an s-triazine in the place of every C atom. •Using s-triazine as a building block. METHOD Methods of Calculations: •Structural, vibrational electronic: DFT, Gaussian-16 [7]; Functionals: ωB97X-D [8], MN15[9] Basis set: 6-311G(d,p) •For Thermal stability: molecular dynamics (LAMMPS code [10]); ReaX-FF [11,12] ●A novel family of structures, the porous carbon nitride fullerenes, is proposed. ●These cage molecules are thermodynamically, electronically and thermally stable. ●They may exhibit interesting properties inherited from their 2D counterparts ●The low formation energy with respect to their 2D counterparts is a strong indication for their synthesis. 1. Bond lengths and other distances (Å): C60N60 C120N60 Electron density of all HOMO orbitals One of the LUMO orbitals Total electron density 3. Electronic Properties: The large •ionization potential (IP), •HOMO-LUMO (H-L) gap and •chemical hardness η=(IP-EA)/2 indicate very stable electronic state 4. Thermal stability: C60N60,C120N60: thermally stable well above 1000 and 2000 K, respectively Test of linearity of average energy vs temperature 2. Vibrational Properties: IR RAMAN ε = molar absorptivity ACKNOWLEDGEMENTS [1] Z.G. Fthenakis, N. N. Lathiotakis, Nanoscale Horiz., 2025,10, 1184-1191 [2] L. Tan, C. Nie, et al., J. Mater. Chem. A, 2021, 9, 17 —33. [3] J. Mahmood, E. K. Lee et al., Nat. Commun., 2015, 6 , 6486 [4] S. S. Shinde, C. H. Lee, et al., ACS Nano, 2018, 12 , 596 —608 [5] N. Fechler , N. P. Zussblatt , et al., Adv. Mater., 2016, 28 , 1287 —1294 [6] C. Moreira Da Silva, M. Vallet, et al., Sci. Rep., 2023, 13 , 15423 [7] https://gaussian.com/gaussian16 [8] J.-D. Chai and M. Head-Gordon , Phys. Chem. Chem. Phys., 2008, 10 , 6615 —6620 [9] H. S. Yu, X. He, S. L. Li and D. G. Truhlar, Chem. Sci., 2016, 7, 5032 —5051 [10] https://www.lammps.org/ [11] M. Kowalik, C. Ashraf, et al., J. Phys. Chem. B, 2019, 123 , 5357 —5367 [12] Z. G. Fthenakis, I. D. Petsalakis, et al., Front. Chem., 2022, 10 , 951261 PRIN 2022 - Cod. 202278NHAM (PE11) CHERICH-C “Chemical and electrochemical energy storage materials from organic wastes: the treasure hidden in C-based materials” - CUP B53D23008590006, funded by the European Union – Next Generation EU C60N60 Composed of C3N3 hexagons Same stoichiometry as gCN C120N60 Composed of C4N2 hexagons Same stoichiometry as gC2N CONTACT/ARTICLE E-mail: [email protected], [email protected] Article: Z.G. Fthenakis, N. N. Lathiotakis, Nanoscale Horiz., 2025,10, 1184-1191 ArxiV: https://arxiv.org/abs/2410.07822 ε = molar absorptivity