Heteroleptic diimine copper(i) complexes with large extinction coefficients: synthesis, quantum chemistry calculations and physico-chemical properties.
Résumé
: Using the HETPHEN approach, five new heteroleptic copper(i) complexes composed of a push-pull 4,4'-styryl-6,6'-dimethyl-2,2'-bipyridine ligand and a bulky bis[(2-diphenylphosphino)phenyl]-ether (DPEphos) or a bis2,9-mesityl phenanthroline (Mes2Phen) were prepared and characterized by electronic absorption spectroscopy, electrochemistry, and TD-DFT calculations. These complexes exhibit very intense absorption bands in the visible region with extinction coefficient in the range of 5-7 × 10(4) M(-1) cm(-1). The analysis of the position, intensity and band shape indicates a strong contribution from an intra-ligand charge-transfer transition centered on the styrylbipyridine ligand along with MLCT transitions. These new complexes experimentally demonstrate that good light harvesting properties with bis-diimine copper(i) complexes are a reality if one chooses suitable ligands in the coordination sphere. This constitutes a milestone towards using bis-diimine copper(i) complexes for solar energy conversion (artificial photosynthesis and solar cells).
Domaines
Chimie inorganique
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Heteroleptic-ms_DT-ART-05-2013-051288-accepted.pdf (686.76 Ko)
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