title: Effect of meso-substituents on the electronic transitions of BODIPY dyes: DFT and RI-CC2 study.
abstract: In this work, the influence of substituents on the electronic transitions of model 8-R-BODIPY dyes (R=NMe2, NH2, OH, CH3, H, F, SH, Cl, Br, CF3, CN, and NO2) was investigated theoretically using time-dependent density functional theory (TD-DFT) and ab initio coupled-cluster doubles (CC2) quantum chemical calculations. Quantum chemical modeling shows a direct relationship between the electron donating and electron withdrawing character of substituents expressed by Hammett substituent constants (σp) and changes in energy of the HOMO-LUMO gap modulating spectral shifts of the S0→S1 transition. Good linear correlations of the calculated LUMO energies and σp as well as the shape of the HOMO and LUMO allow to obtain a reasonable explanation for the observed effects of substituents.
authors.affiliation: Physical and Technical Institute, Irkutsk State Technical University, 83 Lermontov st., Irkutsk 664074, Russia. Electronic address: igor.petrushenko@istu.edu.
authors.forename: I K
authors.initials: IK
authors.lastname: Petrushenko
authors.affiliation: AE Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 1 Favorsky st., Irkutsk 664033, Russia. Electronic address: ko_petr@irioch.irk.ru.
authors.forename: K B
authors.initials: KB
authors.lastname: Petrushenko
mesh_terms: D001896:Boron Compounds / Q000737:chemistry*; D004396:Coloring Agents / Q000737:chemistry*; D004583:Electrons; D008958:Models, Molecular; D011789:Quantum Theory; D012044:Regression Analysis; D012997:Solvents / Q000737:chemistry
chemical_list: C095489:4,4-difluoro-4-bora-3a,4a-diaza-s-indacene; D001896:Boron Compounds; D004396:Coloring Agents; D012997:Solvents
keywords: Ab initio; BODIPY; DFT; Effect of meso-substituents; Electronic spectrum