Three Novel Interpenetrating Diamondoid Networks from Self-Assembly of 1,12-Dodecanedinitrile with Silver(I) Salts

The self-assembly of 1,12-dodecanedinitrile (ddn) with various silver salts (NO(3)(-), PF(6)(-), AsF(6)(-), ClO(4)(-)) afforded new polymeric coordination networks with the general formula [Ag(ddn)(2)]X. All these species contain interpenetrating diamondoid nets showing interesting features: with X=NO(3)(-) the cationic [Ag(ddn)(2)](+) network exhibits the highest interpenetration (tenfold) ever found within diamondoid nets exclusively based on coordinative bonds. When X=PF(6)(-) or AsF(6)(-) an eightfold diamondoid network is obtained that shows an unusual [4+4] mode of interpenetration, instead of the "normal" set of eight nets equally translated along a principal axis of the adamantanoid cages. The polymeric species that forms with X=ClO(4)(-) is a fourfold interpenetrating diamondoid network; the lower degree of interpenetration in this case is related to the conformation assumed by the flexible ddn ligands.