ChemInform Abstract: WECHSELWIRKUNG VON UEBERGANGSMETALLIONEN MIT PHOTOANGEREGTEN ZUSTAENDEN VON FLAVINEN, FLUORESZENZLOESCHUNG

Varnes, Arthur W.; Dodson, R. Barry; Wehry, Ε. L.

doi:10.1002/chin.197216065

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“…A potential problem with the proposed experimental design is the fluorescence quenching ability of nickel compounds. 13 Although most quenching studies have dealt with inorganic and organometallic derivatives of nickel(II), it was important to eliminate the possibility of quenching for the nickel(III) and -(IV) metallacarborane complexes presented here. Before the syntheses of pyrene-substituted nickelacarboranes are undertaken, the pyrene fluorescence in the presence of both unsubstituted nickel(III) and -(IV) metallacarborane complexes was examined.…”

Section: ■ Resultsmentioning

confidence: 99%

Direct Observation of Bis(dicarbollyl)nickel Conformers in Solution by Fluorescence Spectroscopy: An Approach to Redox-Controlled Metallacarborane Molecular Motors

et al. 2014

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As a continuation of work on metallacarborane-based molecular motors, the structures of substituted bis(dicarbollyl)nickel complexes in Ni(III) and Ni(IV) oxidation states were investigated in solution by fluorescence spectroscopy. Symmetrically positioned cage-linked pyrene molecules served as fluorescent probes to enable the observation of mixed meso-trans/dl-gauche (pyrene monomer fluorescence) and dl-cis/dl-gauche (intramolecular pyrene excimer fluorescence with residual monomer fluorescence) cage conformations of the nickelacarboranes in the Ni(III) and Ni(IV) oxidation states, respectively. The absence of energetically disfavored conformers in solution--dl-cis in the case of nickel(III) complexes and meso-trans in the case of nickel(IV)--was demonstrated based on spectroscopic data and conformer energy calculations in solution. The conformational persistence observed in solution indicates that bis(dicarbollyl)nickel complexes may provide attractive templates for building electrically driven and/or photodriven molecular motors.

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Section: ■ Resultsmentioning

confidence: 99%