Crystal Engineering of Cation-Radical Salts with Weakly Coordinating Carbadodecaborate Anions

Abstract

An X-ray structural analysis revealed that the salts of N,N,N′,N′-tetramethyl-p-phenylenediamine (TMPD), N-methylphenothiazine (MPTZ), and octamethylbiphenylene (OMB), with dodecamethyl- or hexabromo-substituted carbadodecaborate anions, comprise layers of the (partially) oxidized organic donors separated by sheets of the bulky counter-ions. The cationic layers comprise either well-separated TMPD+ or MPTZ+ cation radicals or π-stacks of partially oxidized OMB moieties consisting of more or less distinct (OMB)2+ units. Quantum mechanical calculations revealed that the formation of essentially isolated cation-radical or π-bonded associations in the salts with these weakly coordinating anions is correlated with the strength of the multicenter π-bonding between cation radicals. This pancake bonding is determined by the balance of the electrostatic repulsion between cationic counterparts and attractive dispersion and weakly covalent interactions.