New Cu(I) Coordination Complexes Based on Tetrathiafulvalene Substituted Triazol‐pyridine Ligand: Synthesis,Properties and Theoretical Studies |
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| Authors: | Dong Xia Lin Li Wen‐Feng Cheng Kai‐Xiu Li Feng Cui Zhi‐Gang Niu |
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| Affiliation: | College of Chemistry and Chemical Engineering, Hainan Normal University, Haikou 571158, P.R. China |
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| Abstract: | Two Cu(I) complexes based on the thioethyl‐bridged triazol‐pyridine ligand with tetrathiafulvalene unit (TTF‐TzPy, L ), Cu(I)(Binap)(L)]BF4 ( 5 , Binap=2,2’‐bis(diphenylphosphino)‐1,1’‐binaphthyl) and Cu(I)(Xantphos)(L)]BF4 ( 6 , Xantphos=9,9‐dimethyl‐4,5‐bis(diphenylphosphino)‐xanthene), have been synthesized. All new compounds are characterized by elemental analyses, 1H NMR and mass spectroscopies. The complex 5 has been determined by X‐ray structure analyses which shows that the central copper (I) ion assumes distorted tetrahedral geometry. The photophysical, computational and electrochemical properties of L and 5 ‐ 6 have been investigated. The most representative molecular orbital energy‐level diagrams and the spin‐allowed singlet? singlet electronic transitions of the three compounds have been calculated with density functional theory (DFT) and time‐dependent DFT (TD‐DFT). The luminescence bands of Cu(I) complexes 5 ‐ 6 have been assigned as mixed intraligand and metal‐to‐ligand charge transfer 3(MLCT+π→π*) transitions through analysis of the photophysical properties and DFT calculations. The electrochemical studies reveal that 5 ‐ 6 undergo reversible TTF/TTF+?/TTF2+ redox processes and one irreversible Cu+→Cu2+ oxidation process. |
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| Keywords: | Copper(I) complexes Tetrathiafulvalene Triazol‐pyridine ligands Redox chemistry DFT calculations |
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