Self-assembly of rings, catenanes, and a doubly braided catenane containing gold(I): the hinge-group effect in diacetylide ligands.

Reaction of the flexible dialkynyldigold(I) precursors X(4-C6H4OCH2C-CAu)2 with 1,4-bis(diphenylphosphino)butane gave complexes of formula [[[mu-X(4-C6H4OCH2CCAu)2[mu-(Ph2PCH2CH2CH2CH2PPh2)]]n]. The complexes exist as 25-membered ring compounds with n = 1 when X = O or S, as [2]catenanes with n = 2 when X = CH2 or CMe2, and as a unique doubly braided [2]catenane, containing interlocked 50-membered rings with n = 4 when X = cyclohexylidene. These compounds form easily and selectively by self-assembly; reasons for the selectivity are also discussed.