Theoretical Investigation on the Photophysical Properties of Model Ruthenium Complexes with Diazabutadiene Ligands [Ru(bpy)3−x(dab)x]2+ (x =
详细信息 查看全文
- 作者：Thomas Guillon ; Martial Boggio-Pasqua ; Fabienne Alary ; Jean-Louis Heully ; Emilie Lebon ; Pierre Sutra ; Alain Igau
- 刊名：Inorganic Chemistry
- 出版年：2010
- 出版时间：October 4, 2010
- 年：2010
- 卷：49
- 期：19
- 页码：8862-8872
- 全文大小：990K
- 年卷期：v.49,no.19(October 4, 2010)
- ISSN：1520-510X
文摘
In this study we report a theoretical comparative study of some photophysical properties in the [Ru(bpy)3−x(dab)x]2+ (x = 0−3) series. Density functional theory calculations, validated by highly correlated ab initio benchmark calculations, were used to investigate the absorption and emission properties of the complexes with x = 1−3. The presence of a 1,4-diaza-1,3-butadiene (dab) ligand dramatically changes these properties because of the strong π-acceptor character of this ligand. As a result, comparing to the reference [Ru(bpy)3]2+ complex previously studied, we observed (i) a strong red-shift of the maximum of the absorption band, (ii) a strong decrease of the emission energy of the lowest triplet metal-to-ligand charge transfer state, with all the [Ru(bpy)3−x(dab)x]2+ (x = 1−3) complexes luminescent in the near-infrared region, while [Ru(bpy)3]2+ emits in the visible region, and (iii) the triplet metal-centered states become inaccessible in all the [Ru(bpy)3−x(dab)x]2+ (x = 1−3) complexes. Consequently, these complexes could be potential candidates for infrared light-emitting diodes and probes.