Wechselwirkungen in Molekülkristallen, 163 [1, 2]. Einfluß der Alkalimetall-Reduktionspotentiale auf die Bildung ihrer Kontaktionenmultipel mit Tetracen- und Decacylen-Polyanionen / Interaction in Molecular Crystals, 163 [ 1,2]. The Influence of Alkaline Metal Reduction Potentials on the Formation of their Contaction Multiples with Tetracene and Decacyclene Polyanions

Abstract

The reduction of selected π-hydrocarbons tetracene and decacyclene by various alkaline metals allowed the crystallization and structure determination of the following five solvent separated or solvent shared contaction multiples: [Tetracene⊖⊖ (Na⊕Diglyme)2], [Tetracene⊖⊖ - (K⊕ Triglyme)2], [Decacyclene• ⊖] [Cs⊕ (Triglyme)2], [Decacyclene•⊖⊖⊖] [Na⊕ (DME)3]3, [Decacyclene⊖⊖⊖⊖ (K⊕Diglyme)4]. These alkaline salts contain a radicalanion M• ⊖ , dianions M⊖⊖ , a radicaltrianion M•⊖⊖⊖ , and a tetraanion M⊖⊖⊖⊖ generated by single or multiple electron transfer. Their structures are discussed in terms of the difference in alkaline metal reduction potentials, the powerful cation solvation, the effects of the anion charges and of the cation radii. Further aspects concern the solvent-shared or solvent-separated cation coordination to the anions, the polyion aggregation and for the radical trianion the experimentally proven and quantumchemically simulated Jahn/Teller distortion. Altogether the investigation adds facets to the knowledge of multielectrontransfer reactions and of selforganisation phenomena of alkaline salts.