Transition metal charge transfer systems

Mononuclear Transition Metal Charge Transfer Systems... 

In heterogeneous photoredox systems also a surface complex may act as the chromophore. This means that in this case not a bimolecular but a unimolecular photoredox reaction takes place, since electron transfer occurs within the lightabsorbing species, i.e. through a ligand-to-metal charge-transfer transition within the surface complex. This has been suggested for instance for the photochemical reductive dissolution of iron(III)(hydr)oxides (Waite and Morel, 1984 Siffert and Sulzberger, 1991). For continuous irradiation the quantum yield is then ... 

The UV/visible absorption spectra of [MoO S4 ]2 (n = 0-2) complexes are dominated by the sulfur-to-metal charge transfer transitions of the anion and these bands often serve to characterize the particular system, even though these absorptions may be correlated with those of the parent anion.4 The reduction in symmetry due to complex formation often leads to a broadening or splitting of the bands and, in the majority of the d transition metal complexes, the lowest energy band is red-shifted by an amount which is dependent both upon the nature of the transition metal and the number of such metals bound per MoviO S4 group. 

An absorption (1030 nun) found in the near-infrared spectrum of this complex arises from a mixed valence transition. Light-induced meial-to-metal charge transfer was predicted by Hush56 for systems of this type before it was observed experimentally. Further, his theory relates the energy of absorption to that required for thenral electron transfer (hv = 4 x Ec) and from this it is possible to calculate the thermal electron transfer rale constant (5 x (08 s-1).57... 

Schematic diagrams appropriate to NMP/TCNQ and TTF/TCNQ are shown in Fig. 30 and are based on experimental studies. Application of the one-dimensional Hubbard model to analyse low and high temperature data for NMP/TCNQ yielded consistent values of U and t. For TTF/TCNQ and HMTSF/TCNQ, the increased cation polarizability is believed to have successfully reduced the strength of the effective electron-electron interaction with the result that a true metal-semiconductor transition is observed at 58 K for TTF/TCNQ which disappears completely for HMTSF/TCNQ. At present the advantages of using complex salts as against simple salts of charge-transfer systems to produce organic metals are not clear, particularly since the...

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