Luminescent Tetranuclear Copper(I) and Gold(I) Heterobimetallic Complexes: A Phosphine Acetylide Amidinate Orthogonal Ligand Framework for Selective Complexation.

The synthesis of phosphine acetylide amidinate stabilized copper(I) and gold(I) heterobimetallic complexes was achieved by reacting ligand [{PhPC≡CC(NDipp)}Li(thf)] (Dipp=2,6-N,N'-diisopropylphenyl) with CuCl and Au(tht))Cl, yielding the eight membered ring [{PhPC≡CC(NDipp)}Cu] and the twelve membered ring [{PhPC≡CC(NDipp)}Au]. {PhPC≡CC(NDipp)}Cu] features a Cu unit, which is bridged by two amidinate ligands, served as a metalloligand to synthesize the heterobimetallic Cu/Au complexes [{(AuX)PhPC≡CC(NDipp)}Cu] (X=Cl, CF). In these reactions, the central ring structure is retained. In contrast, when the twelve membered ring [{PhPC≡CC(NDipp)}Au] was reacted with CuX (X=Cl, Br, I and Mes), the reaction led to the rearrangement of the central ring structure to give [{(AuX)PhPC≡CC(NDipp)}Cu] (X=Cl, Br, I and Mes), which feature the same the eight membered Cu ring as above. These compounds were also synthesized by a one-pot reaction. The luminescent heterobimetallic complexes were further investigated for their photophysical properties.