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

Autor:	Dong-ming Chen, Wen-lou Wang, Fang Chen, Hui‐ling Gao, Guo-hua Yao
Rok vydání:	2012
Předmět:	chemistry.chemical_compound Crystallography Circular dichroism chemistry Absorption spectroscopy Computational chemistry Aryl Protonation Density functional theory Physical and Theoretical Chemistry Corrole Spectroscopy Conformational isomerism
Zdroj:	Chinese Journal of Chemical Physics. 25:281-290
ISSN:	2327-2244 1674-0068
DOI:	10.1088/1674-0068/25/03/281-290
Popis:	The geometries and electronic spectra of a series of N-protonated corroles, including unsubstituted 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 S1) is more stable than the other (denoted as S2, 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 S2 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.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::4422e7ad420e0fbd77898bd09a0181bb https://doi.org/10.1088/1674-0068/25/03/281-290 Zobrazit plný text záznamu