Syntheses and structure characterization of inorganic/organic coordination polymers: Ag(dpa), Co(O 3PH)(4,4′-bpy)(H 2O), Zn(O 3PH)(4,4′-bpy) 0.5 and Mn[O 2PH(C 6H 5)] 2(4,4′-bpy) (dpa=2,2′-dipyridylamine; 4,4′-bpy=4,4′-bipyridine)

Abstract

Four novel coordination polymers: Ag(dpa) I, Co(O 3PH)(4,4′-bpy)(H 2O) II, Zn(O 3PH)(4,4′-bpy) 0.5 III and Mn[O 2PH(C 6H 5)] 2(4,4′-bpy) IV (dpa=2,2′-dipyridylamine; 4,4′-bpy=4,4′-bipyridine), were synthesized by microwave heating and characterized by X-ray crystallography. I crystallizes in monoclinic space group P21 /n with a=11.576(2) Å, b=5.585(2) Å, c=15.243(4) Å, β=109.00(2)°, V=931.8(3) Å 3. II crystallizes in monoclinic Cc space group with a=22.477(7) Å, b=5.280(1) Å, c=10.404(4) Å, β=96.08(3)°, V=1227.8(7) Å 3. III crystallizes in monoclinic P21 /c space group with a=9.758(2) Å, b=7.449(3) Å, c=10.277(2) Å, β=100.02(2)°, V=735.6(4) Å 3. IV crystallizes in monoclinic space group P2/c with a=10.174(1) Å, b=11.817(3) Å, c=18.784(4) Å, β=102.14(1)°, V=2207.8(8) Å 3. I consists of linear metal–metal chains wrapped by dpa ligands. II and III consist of two-dimensional M II(O 3PH) inorganic sheets cross-linked by 4,4′-bpy ligands, while IV is formed by Mn[O 2PH(C 6H 5)] 2 sheets cross-linked by 4,4′-bpy ligands. I exhibits two-step thermal decomposition at ~200 and ~250°C, resulting in the reduction of Ag + to Ag metal. II loses its coordination water at ~100°C, leaving vacant coordination sites at Co 2+ ions, while the original framework remains intact. The removal of 4,4′-bpy in II– IV occurs at elevated temperatures above 250, 200 and 400°C respectively.