Crystal structures and spectroscopic properties of a new zinc phosphite cluster and an unexpected chainlike zinc phosphate obtained by hydrothermal reactions

A new zinc phosphite cluster, Zn2(4,4′-dmbpy)2(H2PO3)41, and a new chainlike zinc phosphate, Zn2(5,5′-dmbpy)2(HPO4)(H2PO4)22, have been synthesized under hydrothermal conditions (4,4′-dmbpy=4,4′-dimethyl-2,2′-dipyridy, 5,5′-dmbpy=5,5′-dimethyl-2,2′-dipyridy). Compound 1 is a molecular zinc phosphite constructed from ZnO3N2 trigonal bipyramids, H2PO3 pseudo-pyramids and 4,4′-dmbpy ligands. Compound 2 possesses a 1D chainlike framework constructed from ZnO3N2 trigonal bipyramids, HPO4 tetrahedra, H2PO4 tetrahedra and 5,5′-dmbpy ligands. Both compounds 1 and 2 exhibit intensive photoluminescence originated from the intraligand π–π* transitions. Crystal data: 1, monoclinic, P21/n  , a=8.0310(7)Å, b=20.2301(5)Å, c=10.8424(2)Å, β=110.857(3)°β=110.857(3)°, V=1646.11(15)Å3, Z=2Z=2, R1=0.0297R1=0.0297, wR1=0.0801wR1=0.0801; 2, triclinic, P  -1, a=11.6875(8)Å, b=12.3498(7)Å, c=13.1759(8)Å, α=64.995(9)°α=64.995(9)°, β=65.952(9)°β=65.952(9)°, γ=65.296(8)°γ=65.296(8)°, V=1502.99(16)Å3, Z=2Z=2, R1=0.0418R1=0.0418, wR1=0.1010wR1=0.1010.

A new molecular zinc phosphite and a new chainlike zinc phosphate have been synthesized under hydrothermal conditions. The two compounds exhibit intensive photoluminescence originated from the intraligand π–π* transitions.Figure optionsDownload as PowerPoint slide