Zoekopdracht:
faculteit: "FNWI" en publicatiejaar: "2004"
| Auteurs | M. Busby, P. Matousek, M. Towrie, I.P. Clark, M. Motevalli, F. Hartl, A. jr. Vlcek | | Titel | Rhenium-to-Benzoylpyridine and Rhenium-to-Bipyridine MLCT Excited States of fac-[Re(Cl)(4-benzoylpyridine)2(CO)3] and fac-[Re(4-benzoylpyridine)(CO)3(bpy)]+: A Time-Resolved Spectroscopic and Spectroelectrochemical Study |
| Tijdschrift | Inorganic Chemistry |
| Jaargang | 43 |
| Jaar | 2004 |
| Nummer | 14 |
| Pagina's | 4523-4530 |
| ISSN | 00201669 |
| Faculteit | Faculteit der Natuurwetenschappen, Wiskunde en Informatica |
| Instituut/afd. | FNWI: Van 't Hoff Institute for Molecular Sciences (HIMS) |
| Trefwoorden | - |
| Samenvatting | The lowest allowed electronic transition of fac-[Re(Cl)(CO)3(bopy)2] (bopy ) 4-benzoylpyridine) has a Re f bopy MLCT character, as revealed by UV-vis and stationary resonance Raman spectroscopy. Accordingly, the lowestlying, long-lived, excited state is Re f bopy 3MLCT. Electronic depopulation of the Re(CO)3 unit and population
of a bopy ð* orbital upon excitation are evident by the upward shift of î(CtO) vibrations and a downward shift of the ketone î(CdO) vibration, respectively, seen in picosecond time-resolved IR spectra. Moreover, reduction of a single bopy ligand in the 3MLCT excited state is indicated by time-resolved visible and resonance Raman (TR3)
spectra that show features typical of bopy¥-. In contrast, the lowest allowed electronic transition and lowest-lying excited state of a new complex fac-[Re(bopy)(CO)3(bpy)]+ (bpy ) 2,2¢-bipyridine) have been identified as Re f bpy MLCT with no involvement of the bopy ligand, despite the fact that the first reduction of this complex is bopy-localized, as was proven spectroelectrochemically. This is a rare case in which the localizations of the lowest MLCT excitation and the first reduction are different. 3MLCT excited states of both fac-[Re(Cl)(CO)3(bopy)2] and fac-[Re(bopy)(CO)3(bpy)]+ are initially formed vibrationally hot. Their relaxation is manifested by picosecond dynamic shifts of î(CtO) IR bands. The X-ray structure of fac-[Re(bopy)(CO)3(bpy)]PF6âCH3CN has been determined. |
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