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

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      https://www.ias.ac.in/article/fulltext/jcsc/114/04/0291-0309

    • Keywords

       

      Molydenum; nitrosyl; non-innocence; spectroelectrochemistry; magnetic exchange; electrochromism

    • 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.

    • Author Affiliations

       

      Jon A McCleverty1 Michael D Ward1

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

       
  • Journal of Chemical Sciences | News

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