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

[Image: see text] In this article, the synthesis, structural studies, and luminescence properties of Cu(I), Ag(I), and Au(I) complexes of pyrimidine-based phosphine [C(4)H(3)N(2)-2-NH(CH(2)PPh(2))] (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}{C(4)H(3)N(2)-2-NH(CH(2)PPh(2))}](∞) (2) and [{CuBr}{C(4)H(3)N(2)-2-NH(CH(2)PPh(2))}](∞) (3) were obtained, whereas CuI afforded tetracopper complex [{CuI}(4){C(4)H(3)N(2)-2-NH(CH(2)PPh(2))}(2)(NCCH(3))(2)] (4) having Cu(4) ladder structure supported by P∩N-bridging coordination of 1. The reaction of 1 with AgOTf yielded unprecedented one-dimensional chain structure [{AgOTf}{C(4)H(3)N(2)-2-NH(CH(2)PPh(2))}](∞) (5), whereas the reaction with AgBF(4) produced a 12-membered dinuclear complex, [{Ag}{C(4)H(3)N(2)-2-NH(CH(2)PPh(2))}](2)[BF(4)](2) (6), with each silver atom having a linear geometry. Gold complex [{AuCl}{C(4)H(3)N(2)-2-NH(CH(2)PPh(2))}](2) (7) was synthesized by reacting 1 with [AuCl(SMe(2))]. 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.