Density Functional Theory Investigation of Structures and Electronic Spectra of N-protonated Corroles  

作　　者：Hui-ling Gao Guo-hua Yao Fang Chen Wen-lou Wang Dong-ming Chen 

机构地区：[1]Department of Chemical Physics, University of Science and Technolo&y of China, Hefei 230026, China

出　　处：《Chinese Journal of Chemical Physics》2012年第3期281-290,373,共11页化学物理学报（英文）

摘　　要：The geometries and electronic spectra of a series of N-protonated corroles, including unsub- stituted H4Cor＋ and meso-triaryl substituted H4TPC＋, H4TpFPC＋, and H4TdCPC＋, were theoretically studied with density functional theory （DFT）. The results indicate that all these compounds have two conformers, one with C2 symmetry （denoted as Sl） is more stable than the other （denoted as $2, C1 symmetry） by 15.8-18.5 kJ/mol. The corrole macrocycles of these compounds show significant out-of-plane deformation. The enantiomerizations of the chiral S1 conformers were found to be a multi-step process with the $2 conformers as the intermediates. Electronic absorption spectra and electronic circular dichroism （ECD） of these compounds were calculated with time-dependent DFT. In comparison with H4Cor＋, the UV- Vis absorptions of meso-triaryl species are significantly red-shifted and their Q bands are enhanced due to the π-π conjugation between the aryl and corrole rings. Several neighboring electronic transitions were calculated with opposite signs in rotatory strengths, suggesting that ECD spectroscopy may be a useful tool in studying the electronic transitions of these compounds.

关 键 词：CORROLE N-protonation Density functional theory ENANTIOMERIZATION Elec-tronic spectrum 

分 类 号：O641.121[理学—物理化学] O613.71[理学—化学]