Diverse Architectures and Luminescence Properties of Group 11 Complexes Containing Pyrimidine-Based Phosphine,...

In this article, the synthesis, structural studies, and luminescence properties of Cu^I, Ag^I, and Au^I complexes of pyrimidine-based phosphine [C₄H₃N₂-2-NH(CH₂PPh₂)] (1) are described. The reactions of 1 with CuX led to the isolation of one-dimensional (1D) chain, tetranuclear ladder, or cyclic derivatives. The structural features of these complexes are greatly influenced by the metal-to-ligand ratio, reaction conditions, and CuX (X = Cl, Br or I) employed. In the case of CuCl and CuBr, one-dimensional coordination polymers [{CuCl}{C₄H₃N₂-2-NH(CH₂PPh₂)}]_∞ (2) and [{CuBr}{C₄H₃N₂-2-NH(CH₂PPh₂)}]_∞ (3) were obtained, whereas CuI afforded tetracopper complex [{CuI}₄{C₄H₃N₂-2-NH(CH₂PPh₂)}₂(NCCH₃)₂] (4) having Cu₄ ladder structure supported by P∩N-bridging coordination of 1. The reaction of 1 with AgOTf yielded unprecedented one-dimensional chain structure [{AgOTf}{C₄H₃N₂-2-NH(CH₂PPh₂)}]_∞ (5), whereas the reaction with AgBF₄ produced a 12-membered dinuclear complex, [{Ag}{C₄H₃N₂-2-NH(CH₂PPh₂)}]₂[BF₄]₂ (6), with each silver atom having a linear geometry. Gold complex [{AuCl}{C₄H₃N₂-2-NH(CH₂PPh₂)}]₂ (7) was synthesized by reacting 1 with [AuCl(SMe₂)]. Compounds 2-4 were also prepared using a pestle and mortar by grinding method in almost quantitative yield. Complex 4 with a Cu···Cu distance of 2.828(5) Å shows high luminescence due to the nonbonded metal···metal interactions.