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Metal-to-metal electron-transfer emission in cyanide-bridged chromium : ruthenium complexes : effects of configurational mixing between ligand field and charge transfer excited states
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.
dc.abstract.en | 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. | pl |
dc.contributor.author | Chen, Yuan-Jang | pl |
dc.contributor.author | Odongo, Onduru S. | pl |
dc.contributor.author | McNamara, Patrick G. | pl |
dc.contributor.author | Szaciłowski, Konrad - 132185 | pl |
dc.contributor.author | Endicott, John F. | pl |
dc.date.accessioned | 2015-08-21T12:17:31Z | |
dc.date.available | 2015-08-21T12:17:31Z | |
dc.date.issued | 2008 | pl |
dc.description.number | 23 | pl |
dc.description.physical | 10921-10934 | pl |
dc.description.volume | 47 | pl |
dc.identifier.doi | 10.1021/ic8011266 | pl |
dc.identifier.eissn | 1520-510X | pl |
dc.identifier.issn | 0020-1669 | pl |
dc.identifier.uri | http://ruj.uj.edu.pl/xmlui/handle/item/14830 | |
dc.language | eng | pl |
dc.language.container | eng | pl |
dc.subtype | Article | pl |
dc.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 | pl |
dc.title.journal | Inorganic Chemistry | pl |
dc.type | JournalArticle | pl |
dspace.entity.type | Publication |