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Vibrational Spectra and Density Functional Theory Calculations of Metallotriphenylcorroles
Hui-ling Gao,Fang Chen,Chun-lei Wang,Guo-bing Wang,Dong-ming Chen*
Author NameAffiliationE-mail
Hui-ling Gao 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  
Chun-lei Wang Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, China  
Guo-bing 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 infrared absorption and Raman scattering spectra were measured for the metallotriph-enylcorroles (MTPCs, M=Cu, Co, Ni, Mn). The ground-state structures and vibrational spectra of MTPCs have been calculated with the density functional theory. The observed Raman and IR bands have been assigned based on the calculation results. Due to the symmetry lowering, the vibrational spectra of MTPCs are much more complex than metal-loporphyrins, and several skeletal modes are found strongly coupled to the phenyl vibrations. The relationship between the Raman/IR frequencies and the structures of TPC ring is in-vestigated. It is found that the vibrations involving the CIαCIα stretch and CαCmstretch are sensitive to the size of corrole core. In particular, the frequency of υ5, which is assigned to CIαCIα stretch in coupling with the CαCm symmetric stretch, increases linearly with the decrease of the corrole core-sizes and may be used as a mark band to evaluate the structural change of the metallocorroles.
Key words:  Metallocorroles, Raman spectrum, Molecular vibration, Density functional theory
FundProject:
三苯基咔咯金属配合物的振动光谱和DFT计算
高慧玲,陈方,王春雷,王国兵,陈东明*
摘要:
对三苯基咔咯金属配合物(MTPC, M=Ni, Cu, Co, Mn)的拉曼和红外光谱进行了实验研究. 用DFT方法计算了其基态几何结构以及红外和拉曼光谱,并基于计算结果对测量到的振动谱带进行了局域坐标归属. 研究发现,由于对称性降低,咔咯金属配合物的振动光谱比卟啉金属配合物更为复杂,若干咔咯骨架振动与苯取代基强烈耦合.考察了拉曼和红外谱带频率变化与咔咯环结构的关系,发现随着环内核尺寸的减小,与CIαCIα键伸缩振动和C?Cm键伸缩振动相关的拉曼谱带频率增加,其中CIαCIα伸缩振动的拉曼谱带对环内核尺寸的变化更为敏感且呈良好的线性关系,可以作为反映金属咔咯骨架结构变化的特征谱带.
关键词:  金属咔咯,拉曼光谱,分子振动,DFT
DOI:10.1063/1674-0068/26/04/398-408
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