Silver pyroarsonates obtained from Ag(I)-mediated in situ condensation of aryl arsonate ligands under solvothermal conditions.

Four new layered silver(I) organoarsonates, namely, [Ag(3)(L(3))(CN)] (1) (H(2)L(3) = (PhAsO(2)H)(2)O), [Ag(3)(L(4))(CN)] (2) (H(2)L(4) = (2-NO(2)-C(6)H(4)-AsO(2)H)(2)O), [Ag(3)(HL(5))(H(2)L(5))] (3) (H(3)L(5) = 3-NO(2)-4-OH-C(6)H(3)-AsO(3)H(2)) and [Ag(2)(HL(5))] (4), were synthesized under solvothermal conditions. During the preparations of 1 and 2, condensation of organoarsonate ligands (H(2)L(1) = Ph-AsO(3)H(2); H(2)L(2) = 2-NO(2)-C(6)H(4)-AsO(3)H(2)) and the decomposition of acetonitrile molecules to cyanide anions occurred. Single crystals of H(2)L(4) ligand and compounds 1-4 were isolated, and their crystal structures have been determined by single crystal X-ray diffraction studies. In 1, the one-dimensional (1D) chains based on Ag(I) ions and {L(3)}(2-) anions are further interconnected by CN(-) into two-dimensional (2D) layers. In 2, adjacent Ag(I) ions within the silver(I) organoarsonate layer are further bridged by µ(4)-CN(-) anions with very short Ag···Ag contacts. In 3, the hexanuclear {Ag(6)O(12)} clusters are interconnected by bridging organoarsonate ligands into a silver(I) arsonate hybrid layer. In 4, the right-handed {Ag(4)O(4)} chains are further interconnected by organoarsonate ligands as well as additional Ag-O-Ag bridges into a novel silver(I) arsonate layer. Compounds 1 and 2 display red and orange-red emissions, respectively, which may be assigned to be an admixture of ligand-to-metal charge transfer (LMCT) and metal-centered (4d-5s/5p) transitions perturbed by Ag(I)···Ag(I) interactions. Upon cooling from room temperature to 10 K, compound 1 exhibits interesting temperature-dependent emissions.