Metal-to-metal electron-transfer emission in cyanide-bridged chromium : ruthenium complexes : effects of configurational mixing between ligand field and charge transfer excited states

doi:10.1021/ic8011266

Metal-to-metal electron-transfer emission in ...

Bibliographic description

title:	Metal-to-metal electron-transfer emission in cyanide-bridged chromium : ruthenium complexes : effects of configurational mixing between ligand field and charge transfer excited states
author:	Chen Yuan-Jang, Odongo Onduru S., McNamara Patrick G., Szaciłowski Konrad , Endicott John F.
Journal title:	Inorganic Chemistry
volume:	47
issue:	23
date of publication:	2008
pages:	10921-10934
ISSN:	0020-1669
eISSN:	1520-510X
DOI:	10.1021/ic8011266
language:	English
Journal language:	English
abstract in english:	Irradiations of the transition metal-to-transition metal charge transfer (MMCT) absorption bands of a series of cyanide-bridged chromium(III)-ruthenium(II) complexes at 77 K leads to near-infrared emission spectra of the corresponding chromium(II)-ruthenium(III) electron transfer excited states. The lifetimes of most of the MMCT excited states increase more than 10-fold when their am(m)ine ligands are perdueterated. These unique emissions have weak, low frequency vibronic sidebands that correspond to the small excited-state distortions in metal-ligand bonds that are characteristic of transition metal electron transfer involving only the non-bonding metal centered d-orbitals suggesting that the excited-state Cr(II) center has a triplet spin configuration. However, most of the electronically excited complexes probably have overall doublet spin multiplicity and exhibit an excitation energy dependent dual emission with the near in energy Cr(III)-centered and MMCT doublet excited states forming an unusual mixed valence pair.
type:	journal article
subtype:	academic paper