DFT Study of the Molecular and Electronic Structure of Metal-Free Tetrabenzoporphyrin and Its Metal Complexes with Zn,Cd, Al,Ga, In |
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| Authors: | Alexey V. Eroshin Arseniy A. Otlyotov Ilya A. Kuzmin Pavel A. Stuzhin Yuriy A. Zhabanov |
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| Affiliation: | 1.Research Institute of Chemistry of Macroheterocyclic Compounds, Ivanovo State University of Chemistry and Technology, 153000 Ivanovo, Russia; (A.V.E.); (A.A.O.); (I.A.K.); (P.A.S.);2.N.N. Semenov Institute of Chemical Physics of Russian Academy of Sciences, Kosygina Street 4, 119991 Moscow, Russia |
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| Abstract: | The electronic and molecular structures of metal-free tetrabenzoporphyrin (H2TBP) and its complexes with zinc, cadmium, aluminum, gallium and indium were investigated by density functional theory (DFT) calculations with a def2-TZVP basis set. A geometrical structure of ZnTBP and CdTBP was found to possess D4h symmetry; AlClTBP, GaClTBP and InClTBP were non-planar complexes with C4v symmetry. The molecular structure of H2TBP belonged to the point symmetry group of D2h. According to the results of the natural bond orbital (NBO) analysis, the M-N bonds had a substantial ionic character in the cases of the Zn(II) and Cd(II) complexes, with a noticeably increased covalent contribution for Al(III), Ga(III) and In(III) complexes with an axial –Cl ligand. The lowest excited states were computed with the use of time-dependent density functional theory (TDDFT) calculations. The model electronic absorption spectra indicated a weak influence of the nature of the metal on the Q-band position. |
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| Keywords: | tetrabenzoporphyrin DFT study molecular and electronic structure chemical bonding |
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