Macrocyclic Gold(I) Complexes with Bridging Diacetylide and Diphosphine Ligands

The new dialkynyldigold(I) complexes [Ar(OCH C≡CAu) ]n {Ar = 1,4-C (CMe -4-C , 4,4’-C and 1,5-C } react with diphosphines LL = Ph P(CH PPh (n = 1 to 6) and trans-Ph PCH=CHPPh to give luminescent macrocyclic digold(I) or tetragold(I) complexes with bridging diphosphine and diacetylide ligands. The digold(I) complex [1,4-C (CMe -4- C OCH C≡CAu) (μ-LL)], with LL = trans-Ph PCH=CHPPh , forms a 28-membered ring, and the rings associate through aurophilic bonding in the solid state. In contrast, the tetragold(I) complex [4,4’-C (OCH C≡CAu) (μ-LL)], with LL = Ph PCH PPh , forms a more rigid 42-membered ring.