RESONANCE RAMAN-SPECTROSCOPY OF RUTHENIUM(II) AND OSMIUM(II) POLYPYRIDYL COMPLEXES CONTAINING THE N-METHYL-4,4'-BIPYRIDINIUM RADICAL (MQ(CENTER-DOT)) AS A LIGAND - EVIDENCE FOR A M(D-PI)-]MQ(CENTER-DOT)(PI-ASTERISK) METAL-TO-LIGAND CHARGE-TRANSFER (MLCT) TRANSITION

被引:12
作者
BATES, WD
CHEN, PY
BIGNOZZI, CA
SCHOONOVER, JR
MEYER, TJ
机构
[1] LOS ALAMOS NATL LAB,BIOSCI & BIOTECHNOL GRP,LOS ALAMOS,NM 87544
[2] UNIV FERRARA,CNR,CTR FOTOREATT & CATALISI,DIPARTIMENTO CHIM,I-44100 FERRARA,ITALY
[3] UNIV N CAROLINA,DEPT CHEM,CHAPEL HILL,NC 27599
关键词
D O I
10.1021/ic00128a039
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Free N-methyl-4,4'-bipyridinium radical (MQ(.)) displays broad, visible absorptions at 360 and 600 nm that can be assigned to pi --> pi* and pi* --> pi* (MQ(.)) transitions. Excitation-dependent resonance Raman measurements on MQ(.), [(bpy)(2)Ru(MQ(.))(2)](2+), and [(bpy)(2)Os(CO)(MQ(.))](2+) indicate that new absorption bands in the complexes are MQ(.)-based and causes significant resonance enhancements for modes affected by a change in the oxidation state at the metal. The new band is assigned to a MII --> (d pi) -->MQ(.)(pi*) metal-to-ligand charge transfer (MLCT) transition.
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页码:6215 / &
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