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 [{Ph 2 PC≡CC(NDipp) 2 }Li(thf) 3 ] (Dipp=2,6-N,N'-diisopropylphenyl) with CuCl and Au(tht))Cl, yielding the eight membered ring [{Ph 2 PC≡CC(NDipp) 2 } 2 Cu 2 ] and the twelve membered ring [{Ph 2 PC≡CC(NDipp) 2 } 2 Au 2 ]. {Ph 2 PC≡CC(NDipp) 2 } 2 Cu 2 ] features a Cu 2 unit, which is bridged by two amidinate ligands, served as a metalloligand to synthesize the heterobimetallic Cu I /Au I complexes [{(AuX)Ph 2 PC≡CC(NDipp) 2 } 2 Cu 2 ] (X=Cl, C 6 F 5 ). In these reactions, the central ring structure is retained. In contrast, when the twelve membered ring [{Ph 2 PC≡CC(NDipp) 2 } 2 Au 2 ] was reacted with CuX (X=Cl, Br, I and Mes), the reaction led to the rearrangement of the central ring structure to give [{(AuX)Ph 2 PC≡CC(NDipp) 2 } 2 Cu 2 ] (X=Cl, Br, I and Mes), which feature the same the eight membered Cu 2 ring as above. These compounds were also synthesized by a one-pot reaction. The luminescent heterobimetallic complexes were further investigated for their photophysical properties.