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Density Functional Theory Investigation of Structures and Electronic Spectra of N-protonated Corroles
Hui-ling Gao,Guo-hua Yao,Fang Chen,Wen-lou Wang,Dong-ming Chen*
Author NameAffiliationE-mail
Hui-ling Gao Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, China  
Guo-hua Yao Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, China  
Fang Chen Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, China  
Wen-lou Wang Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, China  
Dong-ming Chen* Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, China dmchen@ustc.edu.cn 
Abstract:
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 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 in-termediates. 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.
Key words:  Corrole, N-protonation, Density functional theory, Enantiomerization, Elec-tronic spectrum
FundProject:
质子化corroles的结构和电子光谱的密度泛函理论研究
高慧玲,姚国华,陈方,王文楼,陈东明*
摘要:
用电子密度泛函理论研究了N-质子化corrole(H4Cor+)和meso位芳基取代质子化corroles(H4TPC+、H4TpFPC+和H4TdCPC+)的几何构型、内消旋反应机理以及电子光谱. 结果表明,这些化合物均有两种稳定构型(势能面极小),一个为C2对称性的S1(最稳定构型),另一为C1对称性的S2,其中S1的能量比S2低约15.8~18.5 kJ/mol.S1和S2的corrole环都呈现明显的面外扭曲变形. 手性S1的两个对映异构体之间的转化是一个以S2为中间态的多步过程. 用TDDFT计算了它们的紫外可见电子吸收光谱和圆二色谱(ECD). 与H4Cor+相比,H4TPC+、H4TpFPC+和H4TdCPC+的紫外可见吸收都发生了明显红移,且它们的Q带都因芳基取代基与corrole环之间的π-π共轭而明显增强. 计算表明,质子化corrole的若干相邻电子跃迁的旋转强度符号相反,表明ECD谱可能是研究其电子跃迁的有用工具.
关键词:  Corrole,N-质子化,密度泛函理论,消旋反应,电子光谱
DOI:10.1088/1674-0068/25/03/281-290
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