Heteroleptic diimine copper(i) complexes with large extinction coefficients: synthesis, quantum chemistry calculations and physico-chemical properties.

Martina Sandroni (1) , Megumi Kayanuma (2) , Mateusz Rebarz (3) , Huriye Akdas-Kilig (4) , Yann Pellegrin (1) , Errol Blart (1) , Hubert Le Bozec (5) , Chantal Daniel (2) , Fabrice Odobel (1)

1 CEISAM - Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation
2 Institut de Chimie de Strasbourg
3 LASIRE - Laboratoire Avancé de Spectroscopie pour les Intéractions la Réactivité et l'Environnement - UMR 8516
4 ISCR - Institut des Sciences Chimiques de Rennes
5 Organométalliques: Matériaux et Catalyse

: 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

Martina Sandroni, Megumi Kayanuma, Mateusz Rebarz, Huriye Akdas-Kilig, Yann Pellegrin, et al.. Heteroleptic diimine copper(i) complexes with large extinction coefficients: synthesis, quantum chemistry calculations and physico-chemical properties.. Dalton Transactions, 2013, 42 (40), pp.14628-14638. ⟨10.1039/c3dt51288f⟩. ⟨hal-00861248⟩