Application of transient resonance Raman spectroscopy to the structure of a photoinduced electron-transfer intermediate
- Univ. of North Carolina at Chapel Hill, NC (United States)
Transient resonance Raman spectra have been acquired for the chromophore-quencher complexes fac-[(bpy)-Re{sup I}(CO){sub 3}(MQ{sup +})]{sup 2+} and cis-[(bpy){sub 2}Os{sup II}(CO)(MQ{sup +})]{sup 3+} (MQ{sup +} is monoquat, N-methyl-4,4{prime}=bipyridinium cation; bpy is 2,2{prime}-bipyridine) following metal-to-ligand charge-transfer excitation. The transient spectra verify that bpy{sup {sm_bullet}{minus}} {yields} MQ{sup +} intramolecular electron transfer occurs ({tau} < 7 ns) with the excited electron residing ultimately on the monoquat ligand. By comparison to vibrational data for biphenyl, 4,4{prime}-bipyridine, N,N{prime}-dihydro-4,4{prime}-bipyridinium dication, and methyl viologen (paraquat) and their corresponding, one-electron reduced forms, it can be inferred that, in the MQ{sup +}-based MLCT excited state, the electron is delocalized over the entire ligand and the two pyridyl rings assume a coplanar geometry.
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- FG05-86ER13633
- OSTI ID:
- 75744
- Journal Information:
- Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 4 Vol. 33; ISSN 0020-1669; ISSN INOCAJ
- Country of Publication:
- United States
- Language:
- English
Similar Records
Black MLCT absorbers
Solvent control of electronic distribution in the MLCT excited states of ((bpy)(CO) sub 3 Re sup I (4,4 prime -bpy)Re sup I (CO) sub 3 (bpy)) sup 2+