| Autor: |
Durand N; Univ. Rennes, CNRS, ISCR (Institut des Sciences Chimiques de Rennes) UMR 6226, 35000 Rennes, France., Amar A; Univ. Rennes, CNRS, ISCR (Institut des Sciences Chimiques de Rennes) UMR 6226, 35000 Rennes, France.; Laboratoire de Physique et Chimie Quantiques, Faculté des Sciences, Université Mouloud Mammeri de Tizi-Ouzou, Tizi-Ouzou 15000, Algeria., Mhanna R; Institut de Science des Matériaux de Mulhouse CNRS-UMR 7361, Université de Haute Alsace, 15 rue Jean Starcky, 68057 Mulhouse, France., Akdas-Kiliç H; Univ. Rennes, CNRS, ISCR (Institut des Sciences Chimiques de Rennes) UMR 6226, 35000 Rennes, France.; Department of Chemistry, Yildiz Technical University, Esenler, Istanbul 34220, Turkey., Soppera O; Institut de Science des Matériaux de Mulhouse CNRS-UMR 7361, Université de Haute Alsace, 15 rue Jean Starcky, 68057 Mulhouse, France., Malval JP; Institut de Science des Matériaux de Mulhouse CNRS-UMR 7361, Université de Haute Alsace, 15 rue Jean Starcky, 68057 Mulhouse, France., Boucekkine A; Univ. Rennes, CNRS, ISCR (Institut des Sciences Chimiques de Rennes) UMR 6226, 35000 Rennes, France., Fillaut JL; Univ. Rennes, CNRS, ISCR (Institut des Sciences Chimiques de Rennes) UMR 6226, 35000 Rennes, France. |
| Abstrakt: |
One- and two-photon characterizations of a series of hetero- and homoleptic [RuL 3-n (bpy) n ] 2+ ( n = 0, 1, 2) complexes carrying bipyridine π-extended ligands (L), have been carried out. These π-extended D-π-A-A-π-D-type ligands (L), where the electron donor units (D) are based on diphenylamine, carbazolyl, or fluorenyl units, have been designed to modulate the conjugation extension and the donating effect. Density functional theory calculations were performed in order to rationalize the observed spectra. Calculations show that the electronic structure of the π-extended ligands has a pronounced effect on the composition of HOMO and LUMO and on the metallic contribution to frontier MOs, resulting in strikingly different nonlinear properties. This work demonstrates that ILCT transitions are the keystone of one- and two-photon absorption bands in the studied systems and reveals how much MLCT and LLCT charge transfers play a decisive role on the two-photon properties of both hetero- and homoleptic ruthenium complexes through cooperative or suppressive effects. |
