Interaction in molecular crystals, 163. The influence of alkaline metal reduction potentials on the formation of their contaction multiples with tetracene and decacyclene polyanions

The reduction of selected pi -hydrocarbons tetracene and decacyclene by var ious alkaline metals allowed the crystallization and structure determinatio n of the following five solvent separated or solvent shared contaction mult iples: [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 radica lanion M.-, dianions M--, a radicaltrianion M.---, and a tetraanion M---- g enerated by single or multiple electron transfer. Their structures are disc ussed in terms of the difference in alkaline metal reduction potentials, th e powerful cation solvation, the effects of the anion charges and of the ca tion radii. Further aspects concern the solvent-shared or solvent-separated cation coordination to the anions, the polyion aggregation and for the rad ical trianion the experimentally proven and quantumchemically simulated Jah n/Teller distortion. Altogether the investigation adds facets to the knowle dge of multielectrontransfer reactions and of selforganisation phenomena of alkaline salts.