SYNTHESIS, ELECTROCHEMISTRY AND PHOTOEXCITED-STATE PROPERTIES OF DINUCLEAR RUTHENIUM COMPLEXES BRIDGED BY 2,6'-BIS(2-PYRIDYL)-2,2'/6,2''-THIAZOLO[4,5-D]-BENZOTHIAZOLE

被引:25
作者
HAGA, M [1 ]
ALE, MM [1 ]
KOSEKI, S [1 ]
YOSHIMURA, A [1 ]
NOZAKI, K [1 ]
OHNO, T [1 ]
机构
[1] OSAKA UNIV,FAC SCI,DEPT CHEM,TOYONAKA,OSAKA 560,JAPAN
关键词
SPECTROELECTROCHEMISTRY; CHARGE TRANSFER EXCITED STATE; RUTHENIUM COMPLEXES; DINUCLEAR COMPLEXES; MIXED-VALENCE COMPLEXES;
D O I
10.1016/0020-1693(94)04066-4
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The new bridging ligand, 2,6'-bis(2-pyridyl)-2,2': 6,2''-thiazolo[4,5-d]-benzothiazole (bptb) and its dinuclear Ru complexes have been synthesized. The combination of the transient absorption (TA) spectra and spectroelectrochemical difference spectra has led to the assignment of the lowest excited state for the dinuclear Ru(II) complexes as a Ru-to-bptb charge transfer state. Although the ab initio molecular calculations of bridging ligands have provided lower HOMO/LUMO energies for bptb compared to those of 2,6-bis(2-pyridyl)benzodiimidazole (dpimbH(2)), the degree of electronic coupling for the dinuclear bptb complex is smaller than that for the dpimbH(2) complex from the analysis of intervalence charge transfer band. Since both dinuclear Ru complexes have a similar coordination environment, the Ru d pi-HOMO L pi mixing is dominant for the metal-metal interaction through the hole transfer mechanism.
引用
收藏
页码:17 / 24
页数:8
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