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 [{Ph2PC≡CC(NDipp)2}Li(thf)3] (Dipp=2,6‐N,N′‐diisopropylphenyl) with CuCl and Au(tht))Cl, yielding the eight membered ring [{Ph2PC≡CC(NDipp)2}2Cu2] and the twelve membered ring [{Ph2PC≡CC(NDipp)2}2Au2]. {Ph2PC≡CC(NDipp)2}2Cu2] features a Cu2 unit, which is bridged by two amidinate ligands, served as a metalloligand to synthesize the heterobimetallic CuI/AuI complexes [{(AuX)Ph2PC≡CC(NDipp)2}2Cu2] (X=Cl, C6F5). In these reactions, the central ring structure is retained. In contrast, when the twelve membered ring [{Ph2PC≡CC(NDipp)2}2Au2] was reacted with CuX (X=Cl, Br, I and Mes), the reaction led to the rearrangement of the central ring structure to give [{(AuX)Ph2PC≡CC(NDipp)2}2Cu2] (X=Cl, Br, I and Mes), which feature the same the eight membered Cu2 ring as above. These compounds were also synthesized by a one‐pot reaction. The luminescent heterobimetallic complexes were further investigated for their photophysical properties. [ABSTRACT FROM AUTHOR]