高等学校化学学报Issue(6)：1267-1276,10.DOI:10.7503/cjcu20140046
氮混杂金属卟啉吸收光谱性质的理论研究
Theoritical Studies on the Structure and Absorption Spectra of Neo-Confused Metal Porphyrin
摘要
Abstract
On the basis of detailed density functional theory(DFT), the molecular geometrical structures and orbital energy levels of free base porphyrin(FBP) and neo-confused porphyrin(NECP) coordinated with Mg, Ni, Cu, Zn were studied at B3LYP/ 6-31+G(d) level. The electronic absorption spectra of metal coordinated porphyrins were studied in gas phase at time dependent density functional level, including the excitation ener-gy, absorption wavelength, oscillator strength and the orbital composition of the electronic transition. Since the metal coordinated FBPs( M-FBP) have D4h symmetry, HOMO/ HOMO-1, LUMO/ LUMO+1 degenerate re-spectively with the similar orbital energy level. The energy gaps of HOMO-LUMO of M-FBPs are about 3. 0 eV. The structure and orbital properties of M-FBPs evolve strong Soret bands in the absorption spectra. Due to the change of C / N atom in the center structure of NECP, M-NECP molecular frontier orbitals composition is more complicated than that of M-FBP. In M-NECPs, the molecular orbital energy gaps(HOMO-LUMO) re-duce to about 2. 6 eV. The C / N exchange strategy can vary the molecular symmetry and molecular orbital composition of M-NECPs, which leads to the energy level splitting, strong electronic absorption peaks of Soret band and the appearance of Q absorption band. All the parameters of M-FBPs and M-NECPs were investigated in three different solvents(water, chloroform and benzene). Under the solvent conditions, the electronic ab-sorption spectra of M-FBP and M-NECP take place red shift along with the weaken polarity of solvent(water, chloroform, benzene) and enhance the absorption peak intensity.关键词
氮混杂卟啉/金属卟啉/密度泛函理论/含时密度泛函理论/电子吸收光谱Key words
Neo-confused porphyrin/Metal porphyrin/Density functional theory ( DFT)/Time dependent density functional theory(TD-DFT)/Electronic absorption spectrum分类
化学化工引用本文复制引用
宫健,曹洪玉,李慎敏,唐乾,杨彦杰,郑学仿..氮混杂金属卟啉吸收光谱性质的理论研究[J].高等学校化学学报,2014,(6):1267-1276,10.基金项目
国家自然科学基金(批准号:21271036,20871024)和辽宁省教育厅科学技术研究项目(批准号：L2013470, L2013471)资助. Supported by the National Natural Science Foundation of China(Nos.21271036,20871024) and the Science and Technology Project of Liaoning Provincal Department of Education, China(Nos. L2013470, L2013471) （批准号:21271036,20871024）
