MOLECULAR-STRUCTURE AND LINKAGE ISOMERISM OF CIS-[RU(BIPY)2-(TRANS-CR(CYCLAM)(CN)2)2]4+ (BIPY = 2,2'-BIPYRIDINE, CYCLAM = 1,4,8,11-TETRAAZACYCLOTETRADECANE)

被引：31

作者：

BIGNOZZI, CA ^{[1
]}

CHIORBOLI, C ^{[1
]}

INDELLI, MT ^{[1
]}

SCANDOLA, F ^{[1
]}

BERTOLASI, V ^{[1
]}

GILLI, G ^{[1
]}

机构：

[1] UNIV FERRARA,CTR STRUTTURIST DIFFRATTOMETR,DIPARTIMENTO CHIM,I-44100 FERRARA,ITALY

来源：

JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS | 1994年 / 16期

关键词：

D O I：

10.1039/dt9940002391

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The molecular structure of the trinuclear complex cis-[Ru(bipy)2{trans-Cr(cyclam)(CN)2}2]4+ (bipy = 2,2'-bipyridine, cyclam = 1,4,8,11-tetraazacyclotetradecane) has been determined by X-ray diffraction. The co-ordination octahedra of the ruthenium(II) and chromium(III) units are staggered, and a modest deviation from linearity is observed in the Ru-(NC)-Cr units. The binding mode of the bridging cyanides, not obtainable from the crystallographic data, was demonstrated to be -Ru(II)-NC-Cr(III)- by infrared spectroscopy. This binding mode is imposed by synthesis, but is not the thermodynamically stable one. Indeed, linkage isomerization of the bridging ligands can be induced by heating the complex in the solid state (several hours at 150-degrees-C). The flip of the bridging cyanide is clearly detectable by infrared spectroscopy. The photophysical properties of the -Ru(II)-CN-Ce(III)- linkage isomer, featuring efficient transfer of excitation energy from the Ru(bipy)22+ chromophore to the emitting chromium(III) fragment, have been studied.

引用

页码：2391 / 2395

页数：5

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