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 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.