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Photophysical Properties of the Re I and Ru II Complexes of a New C 60 ‐Substituted Bipyridine Ligand
Author(s) -
Armaroli Nicola,
Accorsi Gianluca,
Felder Delphine,
Nierengarten JeanFrançois
Publication year - 2002
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/1521-3765(20020517)8:10<2314::aid-chem2314>3.0.co;2-z
Subject(s) - photochemistry , chemistry , excited state , luminescence , moiety , ruthenium , flash photolysis , phosphorescence , singlet state , ultrafast laser spectroscopy , quenching (fluorescence) , triplet state , electron transfer , bipyridine , photoinduced electron transfer , ligand (biochemistry) , spectroscopy , crystallography , materials science , reaction rate constant , fluorescence , molecule , stereochemistry , crystal structure , atomic physics , organic chemistry , kinetics , receptor , biochemistry , quantum mechanics , catalysis , physics , optoelectronics
The rhenium( I ) and ruthenium( II ) complexes of a fullerene‐substituted bipyridine ligand have been prepared. Electrochemical studies indicate that some ground state electronic interaction between the fullerene subunit and the metal‐complexed moiety are present in the Re I but not the Ru II complex. The photophysical properties have been investigated by steady‐state and time‐resolved UV/Vis‐NIR luminescence spectroscopy and nanosecond laser flash photolysis in CH 2 Cl 2 solution, and compared to those of the corresponding model compounds. Excitation of the methanofullerene moiety in the dyads does not lead to excited state intercomponent interactions. Instead, excitation of the metal‐complexed unit shows that the lowest triplet metal‐to‐ligand‐charge‐transfer excited state ( 3 MLCT) centered on the Re I ‐ or Ru II ‐type unit is quenched with a rate constant of about 2.5×10 8 s −1 . The quenching is attributed to an electron‐transfer (ElT) process leading to the reduction of the carbon sphere, as determined by luminescence spectroscopy for the Ru II dyad. Experimental detection of electron transfer in the Re I dyad is prevented due to the unfavorable absorption of the metal‐complexed moiety relative to the fullerene unit. However, it can be postulated on the basis of energetic/kinetic arguments and by comparison with the Ru II ‐type array. The primary ElT process is followed by charge‐recombination to give the lowest‐lying fullerene triplet excited state ( 3 C 60 ) with quantitative yield, as determined by sensitized singlet oxygen luminescence experiments. Direct 3 MLCT→ 3 C 60 triplet–triplet energy‐transfer (EnT) does not successfully compete with ElT since it is highly exoergonic and located in the Marcus inverted region. The quantum yield of singlet oxygen sensitization ( Φ Δ ) of the Re I ‐based dyad is found to be lower (0.80) than for the corresponding Ru II derivative (1.0). This is likely to be the consequence of different conformational structures for the two dyads, rather than a different yield of 3 C 60 formation.