Unexpected polymeric string formation between Ag(I) and a homoleptic thioether cage: synthesis and crystal structure of [R,R′-S6tricosane] and {[Ag(R,R′-S6hexacosane)]TsO}∞

The large cavity homoleptic thioether cages [R,R′-S6tricosane] (1-hydroxymethyl-9-methyl-3,7,11,15,18,22-hexathiabicyclo[7.7.7]tricosane) (1) and [R,R’-S6hexacosane] (1-hydroxymethyl-10-methyl-3,8,12,17,20,25-hexathiabicyclo-[8.8.8]hexacosane) (2) have been synthesized and the structures of 1 and of the complex {[Ag(2)]TsO}∞ have been elucidated, the latter showing a polymeric string structure with Ag+ coordinated by three different cages.