Bis(1-(4-tolyl)-carboran-2-yl)-(4-tolyl)-borane [(1-(4-MeC6 H4 )-closo-1,2-C2 B10 H10 -2-)2 (4-MeC6 H4 )B] (1), a new bis(o-carboranyl)-(R)-borane was synthesised by lithiation of the o-carboranyl precursor and subsequent salt metathesis reaction with (4-tolyl)BBr2 . Cyclic voltammetry experiments on 1 show multiple distinct reduction events with a one-electron first reduction. In a selective reduction experiment the corresponding paramagnetic radical anion 1.- was isolated and characterized. Single-crystal structure analyses allow an in-depth comparison of 1, 1.- , their calculated geometries, and the S1 excited state of 1. Photophysical studies of 1 show a charge transfer (CT) emission with low quantum yield in solution but a strong increase in the solid state. TD-DFT calculations were used to identify transition-relevant orbitals.
Keywords: Wade's rules; carborane; charge transfer; radical; three-coordinate boron.
© 2021 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.