Diverse Architectures and Luminescence Properties of Group 11 Complexes Containing Pyrimidine-Based Phosphine, N-((Diphenylphosphine)methyl)pyrimidin-2-amine.

In this article, the synthesis, structural studies, and luminescence properties of CuI, AgI, and AuI 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.