Synthesis, Characterization, and Photochemical and Computational Investigations of Ru(II) Heterocyclic Complexes Containing 2,6-dimethylphenylisocyanide (CNx) Ligand
详细信息 查看全文
- 作者：John M. Villegas ; Stanislav R. Stoyanov ; Wei Huang ; Loranelle L. Lockyear ; Joseph H. Reibenspies ; and D. Paul Rillema
- 刊名：Inorganic Chemistry
- 出版年：2004
- 出版时间：October 4, 2004
- 年：2004
- 卷：43
- 期：20
- 页码：6383 - 6396
- 全文大小：334K
- 年卷期：v.43,no.20(October 4, 2004)
- ISSN：1520-510X
文摘
The isocyanide ligand forms complexes with ruthenium(II) bis-bipyridine of the type [Ru(bpy)2(CNx)Cl](CF3SO3) (1),[Ru(bpy)2(CNx)(py)](PF6)2 (2), and [Ru(bpy)2(CNx)2](PF6)2 (3) (bpy = 2,2'-bipyridine, py = pyridine, and CNx =2,6-dimethylphenylisocyanide). The redox potentials shift positively as the number of CNx ligands increases. Themetal-to-ligand charge-transfer (MLCT) bands of the complexes are located at higher energy than 450 nm andblue shift in proportion to the number of CNx ligands. The complexes are not emissive at room temperature butexhibit intense structured emission bands at 77 K with emission lifetimes as high as 25 
mages/entities/mgr.gif">s. Geometry optimizationof the complexes in the singlet ground and lowest-lying triplet states performed using density functional theory(DFT) provides information about the orbital heritage and correlates with X-ray and electrochemical results. Thelowest-lying triplet-state energies correlate well with the 77 K emission energies for the three complexes. Singletexcited states calculated in ethanol using time-dependent density functional theory (TDDFT) and the conductor-likepolarizable continuum model (CPCM) provide information that correlates favorably with the experimental absorptionspectra in ethanol.