Journal of the Chemical Society, Dalton Transactions p. 3333 - 3340 (1993)
Update date:2022-08-17
Topics:
Lowe, Nigel D.
Garner, C. David
The binding of Li(+), Na(+) and K(+) cations to the crown ether rings of a series of transition-metal complexes with crown ether benzodithiolene ligands has been monitored.Fast atom bombardment mass spectrometry and UV/VIS spectroscopy have been used to demonstrate the binding of the cations to the complexes, and cyclic voltammetric studies provide a quantitative measure of the perturbations which result upon cation binding.The results support the view that the electronic transitions arise primarily from sulfur-to-metal charge-transfer transitions, provide information concerning the dithiolate(2-) or dithioketonic form of the dithiolene ligand, and indicate whether a particular redox process is primarily metal- or ligand-based.Some selectivity within the series Li(+), Na(+) and K(+) is observed, with the benzo-15-crown-5 ring showing a preference for the first two and the benzo-18-crown-6 ring preferring K(+).Tris(crown ether benzodithiolene) complexes of molybdenum and tungsten show the most promise as sensors for alkali-metal cations.
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