SITE-SELECTIVE AND STARK SPECTROSCOPY OF THE SERIES [OS(2,2'-BIPYRIDINE)(3-X)(2,2'-BIPYRIDINE-D(8))(X)](2+)(X=0-3) IN SINGLE-CRYSTAL [RU(2,2'-BIPYRIDINE)(3)](PF6)(2) - LOCALIZATION OF AN INTRAMOLECULAR TRIPLET METAL-TO-LIGAND CHARGE-TRANSFER EXCITON BY PARTIAL DEUTERATION

被引:27
作者
RIESEN, H
WALLACE, L
KRAUSZ, E
机构
[1] Research School of Chemistry, Australian National University, Canberra
关键词
D O I
10.1063/1.469530
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
Selective luminescence and excitation spectroscopy and Stark experiments of the title systems are reported. Dramatic differences of the x=1 and x=2 spectra, in comparison with the x=0 and x=3 spectra are observed. The lowest-excited state in the x=1 and x=2 spectra is a charge-transfer excitation localized on the protonated ligand(s). A superposition of "deuterated" and "protonated" transitions is observed for the x=1 and x=2 systems in the excitation spectra. The deuteration shift (≈32 cm-1) is much larger than the excitation exchange interaction β between the metal-ligand subunits. |β| is ≈2 cm-1, as directly determined from the observed splittings (5-7 cm-1) of I, the lowest-energy electronic origin. Stark shifts confirm the charge transfer character of the lowest-excited states. The splittings and relative intensities of the origins and their Stark effect can be quantitatively described by an exciton formalism. © 1995 American Institute of Physics.
引用
收藏
页码:4823 / 4831
页数:9
相关论文
共 28 条
[1]   CRYSTAL AND MOLECULAR-STRUCTURES OF [RU(BPY)3](PF6)3 AND [RU(BPY)3](PF6)2 AT 105-K [J].
BINER, M ;
BURGI, HB ;
LUDI, A ;
ROHR, C .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1992, 114 (13) :5197-5203
[2]  
BRADLEY PG, 1981, J AM CHEM SOC, V103, P7741
[3]   SITE SELECTIVE SPECTRA OF THE LOWEST EXCITED-STATES OF [OS(BPY)3]2+ IN [RU1-XOSX(BPY)3]PF6, [RU1-XOS(BPY)3]ASF6, [RU1-XOS(BPY)3]SBF6 [J].
BRAUN, D ;
GALLHUBER, E ;
HENSLER, G ;
YERSIN, H .
MOLECULAR PHYSICS, 1989, 67 (02) :417-430
[4]   MONO- + BIS-(2,2]-BIPYRIDINE) + )1,10-PHENANTHROLINE) CHELATES OF RUTHENIUM + OSMI17 .4. BIS CHELATES OF BIVALENT + TERVALENT OSMIUM [J].
BUCKINGHAM, DA ;
DWYER, FP ;
GOODWIN, HA ;
SARGESON, AM .
AUSTRALIAN JOURNAL OF CHEMISTRY, 1964, 17 (03) :325-&
[5]  
CAROLL PJ, 1987, J AM CHEM SOC, V109, P7613
[6]  
Craig D.P., 1968, EXCITONS MOL CRYSTAL
[7]   NEUTRAL EXCITATION MODEL FOR TRIPLET FACTOR GROUP SPLITTINGS IN AROMATIC CRYSTALS [J].
CRAIG, DP ;
SOMMER, BS .
CHEMICAL PHYSICS LETTERS, 1973, 22 (02) :239-242
[8]  
FISCHER G, 1973, SYNTHESIS-STUTTGART, P218
[9]   HIGHLY RESOLVED EMISSION OF [OS(BPY-H8)N(BPY-D8)3-N]2+ (N=0-3) - EVIDENCE FOR ELECTRONIC DELOCALIZATION [J].
HUBER, P ;
YERSIN, H .
JOURNAL OF PHYSICAL CHEMISTRY, 1993, 97 (49) :12705-12709
[10]   LUMINESCENCE OF RUTHENIUM(II) TRIS CHELATE COMPLEXES CONTAINING THE LIGANDS 2,2'-BIPYRIDINE AND 2,2'-BIISOQUINOLINE - BEHAVIOR OF THE RU(BPY)2+ AND RU(BPY)22+ EMITTING UNITS [J].
JURIS, A ;
BARIGELLETTI, F ;
BALZANI, V ;
BELSER, P ;
VONZELEWSKY, A .
INORGANIC CHEMISTRY, 1985, 24 (02) :202-206