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

Authors
  • McCleverty, Jon A.1
  • Ward, Michael D.1
  • 1 University of Bristol, School of Chemistry, Cantocks Close, Bristol, BS8 1TS, UK , Bristol
Type
Published Article
Journal
Journal of Chemical Sciences
Publisher
Springer India
Publication Date
Aug 01, 2002
Volume
114
Issue
4
Pages
291–309
Identifiers
DOI: 10.1007/BF02703822
Source
Springer Nature
Keywords
License
Yellow

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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