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The new dialkynyldigold(I) complexes [Ar(OCH 2 C≡CAu) 2 ]n {Ar = 1,4-C 6 H 4 (CMe 2 -4-C 6 H 4 ) 2 , 4,4’-C 6 H 4 C 6 H 4  and 1,5-C 10 H 6 } react with diphosphines LL = Ph 2 P(CH 2 ) n PPh 2  (n = 1 to 6) and trans-Ph 2 PCH=CHPPh 2  to give luminescent macrocyclic digold(I) or tetragold(I) complexes with bridging diphosphine and diacetylide ligands. The digold(I) complex [1,4-C 6 H 4 (CMe 2 -4- C 6 H 4 OCH 2 C≡CAu) 2 (μ-LL)], with LL = trans-Ph 2 PCH=CHPPh 2 , 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 6 H 4 C 6 H 4 (OCH 2 C≡CAu) 2 (μ-LL)], with LL = Ph 2 PCH 2 PPh 2 , forms a more rigid 42-membered ring.

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