Metal-to-ligand charge transfer absorption in a rhenium(I) complex that contains a π-conjugated bipyridine acceptor ligand

被引:31
作者
Walters, KA
Premvardhan, LL
Liu, Y
Peteanu, LA
Schanze, KS
机构
[1] Univ Florida, Dept Chem, Gainesville, FL 32611 USA
[2] Carnegie Mellon Univ, Dept Chem, Pittsburgh, PA 15213 USA
基金
美国国家科学基金会;
关键词
D O I
10.1016/S0009-2614(01)00318-9
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
This Letter describes a study of the absorption and electroabsorption spectroscopy of a complex consisting of the -Re-1(CO)(3)Cl chromophore coordinated to the 4,4'-{bis-[2,5-(dimethoxyphenyl)ethynyl]}-2,2'-bipyridine ligand. The objective of the study is to explore whether Re --> bipyridine metal-to-ligand charge transfer (MLCT) excitation leads to electron delocalization into the pi -conjugated 2.5-(dimethoxyphenyl)ethynylene moieties. The results indicate that the two low-energy absorption bands observed for the complex have a strong degree of charge transfer character: however, the bands are dominated by intraligand (IL) pi,pi* transitions. The spectroscopic data are consistent with possible configuration mixing between the lowest IL pi, pi* and MLCT transitions. (C) 2001 Published by Elsevier Science B.V.
引用
收藏
页码:255 / 262
页数:8
相关论文
共 25 条
[1]   CHROMOPHORIC FINE TUNING AND THE INTERCHROMOPHORIC COUPLING MODEL IN RUTHENIUM(II) POLYPYRIDYL COMPLEXES [J].
BLAKLEY, RL ;
MYRICK, ML ;
PITTMAN, R ;
DEARMOND, MK .
JOURNAL OF PHYSICAL CHEMISTRY, 1990, 94 (12) :4804-4809
[2]  
Borden W.T., 1975, MODERN MOL ORBITAL T
[3]   Electroabsorption spectroscopy of charge transfer states of transition metal complexes [J].
Brunschwig, BS ;
Creutz, C ;
Sutin, N .
COORDINATION CHEMISTRY REVIEWS, 1998, 177 :61-79
[4]   Effects of intraligand electron delocalization, steric tuning, and excited-state vibronic coupling on the photophysics of aryl-substituted bipyridyl complexes of Ru(II) [J].
Damrauer, NH ;
Boussie, TR ;
Devenney, M ;
McCusker, JK .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1997, 119 (35) :8253-8268
[5]   SPECTRA OF COMPLEXES OF CONJUGATED LIGANDS .2. CHARGE-TRANSFER IN SUBSTITUTED PHENANTHROLINE COMPLEXES - INTENSITIES [J].
DAY, P ;
SANDERS, N .
JOURNAL OF THE CHEMICAL SOCIETY A -INORGANIC PHYSICAL THEORETICAL, 1967, (10) :1536-&
[6]   A study on delocalization of MLCT excited states by rigid bridging ligands in homometallic dinuclear complexes of ruthenium(II) [J].
Hammarstrom, L ;
Barigelletti, F ;
Flamigni, L ;
Indelli, MT ;
Armaroli, N ;
Calogero, G ;
Guardigli, M ;
Sour, A ;
Collin, JP ;
Sauvage, JP .
JOURNAL OF PHYSICAL CHEMISTRY A, 1997, 101 (48) :9061-9069
[7]   Orbital specific charge transfer distances, solvent reorganization energies, and electronic coupling energies: Electronic stark effect studies of parallel and orthogonal intervalence transfer in (NC)(5)Os-II-CN-Ru-III(NH3)(5)(-) [J].
Karki, L ;
Hupp, JT .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1997, 119 (17) :4070-4073
[8]   Electroabsorption studies of intervalence charge transfer in (NC)(5)FeCNOs(NH3)(5)(-): Experimental assessment of charge-transfer distance, solvent reorganization, and electronic coupling parameters [J].
Karki, L ;
Lu, HP ;
Hupp, JT .
JOURNAL OF PHYSICAL CHEMISTRY, 1996, 100 (39) :15637-15639
[9]   Electroabsorption studies of metal-to-ligand charge transfer in Ru(phenanthroline)(3)(2+): Evidence for intrinsic charge localization in the initially formed excited state [J].
Karki, L ;
Hupp, JT .
INORGANIC CHEMISTRY, 1997, 36 (15) :3318-3321
[10]   Transition metals in polymeric π-conjugated organic frameworks [J].
Kingsborough, RP ;
Swager, TM .
PROGRESS IN INORGANIC CHEMISTRY, VOL 48, 1999, 48 :123-231