TY - JOUR
T1 - Structures and spectroscopic properties of meso-tetrasubstituted porphyrin complexes
T2 - Meso-substitutional and central metallic effect study based on density functional theory calculations
AU - Yao, Ping
AU - Han, Shenghao
AU - Zhang, Yuexing
AU - Zhang, Xianyao
AU - Jiang, Jianzhuang
N1 - Funding Information:
Financial support from the Natural Science Foundation of China (Grant Nos. 60676041 and 10778701), Ministry of Education of China, and Shandong University is gratefully acknowledged. We are also grateful to the Shandong Province High Performance Computing Centre for a grant of computer time.
PY - 2009/7/20
Y1 - 2009/7/20
N2 - Effects of the meso-substituents and central metals on the molecular structures, atomic charges, molecular orbital energy gaps, electronic absorption spectra, and infrared (IR) spectra of 12 meso-tetrasubstituted porphyrin complexes including metal-free porphyrins H2P or (Por = TPP, TFPP, TClPP, TPyP) (1-4) and their metal complexes MPor (M = Mg, Zn; Por = TPP, TFPP, TClPP, TPyP) (5-12) [TPP = meso-tetrakis(phenyl)porphyrinate; TFPP = meso-tetrakis(4-fluorophenyl)porphyrinate; TClPP = meso-tetrakis(4-chlorophenyl)porphyrinate; TPyP = meso-tetrakis(4-pyridyl) porphyrinate] are systematically studied by density functional theory calculations at the B3LYP/6-31G(d) level. Good consistency was found between the calculated molecular structures and the experimental X-ray crystallography ones for 1, 3, and 4, and between the simulated electronic absorption and IR spectra and the experimental ones for 1 and 4. The calculation results reveal that introducing substituents at the meso positions of porphyrin induces increasing change in the molecular structures, atomic charges distribution, HOMO and LUMO energy, electronic absorption spectra, and IR spectra along with the increase in the electron-withdrawing ability of substituents in the order of phenyl, 4-fluorophenyl, 4-chlorophenyl, and pyridyl group. Furthermore, the central metal in porphyrins displays much significant influence on the structure and spectroscopic properties of meso-substituted porphyrin complexes. The electronic absorption and IR spectra of 1-12 are compared and assigned in detail. The present work should be not only helpful towards understanding the meso-substitutional and central metallic effects on the structure and spectroscopic properties of meso-substituted porphyrin complexes, but also useful in correctly assigning electronic absorption and IR spectra for porphyrin complexes.
AB - Effects of the meso-substituents and central metals on the molecular structures, atomic charges, molecular orbital energy gaps, electronic absorption spectra, and infrared (IR) spectra of 12 meso-tetrasubstituted porphyrin complexes including metal-free porphyrins H2P or (Por = TPP, TFPP, TClPP, TPyP) (1-4) and their metal complexes MPor (M = Mg, Zn; Por = TPP, TFPP, TClPP, TPyP) (5-12) [TPP = meso-tetrakis(phenyl)porphyrinate; TFPP = meso-tetrakis(4-fluorophenyl)porphyrinate; TClPP = meso-tetrakis(4-chlorophenyl)porphyrinate; TPyP = meso-tetrakis(4-pyridyl) porphyrinate] are systematically studied by density functional theory calculations at the B3LYP/6-31G(d) level. Good consistency was found between the calculated molecular structures and the experimental X-ray crystallography ones for 1, 3, and 4, and between the simulated electronic absorption and IR spectra and the experimental ones for 1 and 4. The calculation results reveal that introducing substituents at the meso positions of porphyrin induces increasing change in the molecular structures, atomic charges distribution, HOMO and LUMO energy, electronic absorption spectra, and IR spectra along with the increase in the electron-withdrawing ability of substituents in the order of phenyl, 4-fluorophenyl, 4-chlorophenyl, and pyridyl group. Furthermore, the central metal in porphyrins displays much significant influence on the structure and spectroscopic properties of meso-substituted porphyrin complexes. The electronic absorption and IR spectra of 1-12 are compared and assigned in detail. The present work should be not only helpful towards understanding the meso-substitutional and central metallic effects on the structure and spectroscopic properties of meso-substituted porphyrin complexes, but also useful in correctly assigning electronic absorption and IR spectra for porphyrin complexes.
KW - Density functional theory
KW - Electronic absorption spectra
KW - Infrared spectra
KW - Porphyrin
KW - Substitutional effect
UR - http://www.scopus.com/inward/record.url?scp=67349280244&partnerID=8YFLogxK
U2 - 10.1016/j.vibspec.2008.09.013
DO - 10.1016/j.vibspec.2008.09.013
M3 - Article
AN - SCOPUS:67349280244
SN - 0924-2031
VL - 50
SP - 169
EP - 177
JO - Vibrational Spectroscopy
JF - Vibrational Spectroscopy
IS - 2
ER -