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Innocent or guilty? Redox activity in and magnetic and optical behaviour of dinuclear molydenum complexes

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Abstract

The phenomenon of ‘non-innocence’, first articulated by Jørgensen in 1966, is briefly reviewed. Spectroelectrochemical studies of a range of dinuclear complexes of the type [Mo(NO)Tp*Cl2(bridge)] (bridge = dipyridyls) and [Mo(O)Tp*Cl2(bridge)] (bridge = diphenolates) which are redox active, show that oxidised or reduced forms of these species exhibit ‘non-innocence’. The spectral behaviour is associated with metal-to-ligand or ligand-to-metal charge transfer phenomena, probably the first time that monodentate bridging ligands have been implicated in ‘non-innocent’ behaviour. These bridging ligands also determine the nature and extent of magnetic interaction between the unpaired spins in [Mo(NO)Tp*Cl2(bridge)] and [Mo(O)Tp*Cl2(bridge)], the dominant mechanism of spin-exchange relying on the extent of {ie291-01}-delocalisation within the bridging ligands. The unusual optical behaviour of these dinuclear complexes when oxidised (oxomolybdenum diphenolates) or reduced (nitrosyl molybdenum dipyridyls) has led to the exploration of electrochromism as a means to develop variable optical attenuators operating in the near-infrared region.

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  1. School of Chemistry, University of Bristol, Cantocks Close, BS8 1TS, Bristol, UK

    Jon A. McCleverty & Michael D. Ward

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  1. Jon A. McCleverty
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  2. Michael D. Ward
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Correspondence to Jon A. McCleverty.

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McCleverty, J.A., Ward, M.D. Innocent or guilty? Redox activity in and magnetic and optical behaviour of dinuclear molydenum complexes. J Chem Sci 114, 291–309 (2002). https://doi.org/10.1007/BF02703822

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