TY - JOUR
T1 - Syntheses, structures, ionic conductivities, and magnetic properties of three new transition-metal borophosphates Na5(H3O){M II3[B3O3(OH)]3(PO 4)6}·2H2O (MII = Mn, Co, Ni)
AU - Yang, Miao
AU - Yu, Jihong
AU - Di, Jiancheng
AU - Li, Jiyang
AU - Chen, Peng
AU - Fang, Qianrong
AU - Chen, Yan
AU - Xu, Ruren
PY - 2006/5/1
Y1 - 2006/5/1
N2 - Three new open-framework transition-metal borophosphates Na 5(H3O){MII3[B3O 3(OH)]3(PO4)6}·2H 2O (MII = Mn, Co, Ni) (denoted as MBPO-CJ25) have been synthesized under mild hydrothermal conditions. Single-crystal X-ray diffraction analyses reveal that the three compounds possess isostructural three-dimensional (3D) open frameworks with one-dimensional 12-ring channels along the [001] direction. Notably, the structure can also be viewed as composed of metal phosphate layers [MII(PO4)2] 4- with Kagomé topology, which are further connected by [B3O7-(OH)] triborates, giving rise to a 3D open framework. The guest water molecules locate in the 12-ring channels. Partial Na+ ions reside in the 10-ring side pockets within the wall of the 12-ring channels, and the other Na+ ions and protonated water molecules locate in the 6-ring windows delimited by MO6 and PO 4 polyhedra to compensate for the negative charges of the anionic framework. These compounds show a high thermal stability and are stable upon calcinations at ca. 500°C. Ionic conductivities, due to the motion of Na+ ions, are measured for these three compounds. They have similar activation energies of 1.13-1.25 eV and conductivities of 2.7 × 10 -7-9.9 × 10-7 S cm-1 at 300°C. Magnetic measurements reveal that there are very weak antiferromagnetic interactions among the metal centers of the three compounds. Crystal data: MnBPO-CJ25, hexagonal, P63/m (No. 176), a = 11.9683(5) Å, c = 12.1303(6) Å, and Z = 2; CoBPO-CJ25, hexagonal, P63/m (No. 176), a = 11.7691(15) Å, c = 12.112(2) Å, and Z = 2; NiBPO-CJ25, hexagonal, P63/m (No. 176), a = 11.7171(5) Å, c = 12.0759(7) Å, and Z = 2.
AB - Three new open-framework transition-metal borophosphates Na 5(H3O){MII3[B3O 3(OH)]3(PO4)6}·2H 2O (MII = Mn, Co, Ni) (denoted as MBPO-CJ25) have been synthesized under mild hydrothermal conditions. Single-crystal X-ray diffraction analyses reveal that the three compounds possess isostructural three-dimensional (3D) open frameworks with one-dimensional 12-ring channels along the [001] direction. Notably, the structure can also be viewed as composed of metal phosphate layers [MII(PO4)2] 4- with Kagomé topology, which are further connected by [B3O7-(OH)] triborates, giving rise to a 3D open framework. The guest water molecules locate in the 12-ring channels. Partial Na+ ions reside in the 10-ring side pockets within the wall of the 12-ring channels, and the other Na+ ions and protonated water molecules locate in the 6-ring windows delimited by MO6 and PO 4 polyhedra to compensate for the negative charges of the anionic framework. These compounds show a high thermal stability and are stable upon calcinations at ca. 500°C. Ionic conductivities, due to the motion of Na+ ions, are measured for these three compounds. They have similar activation energies of 1.13-1.25 eV and conductivities of 2.7 × 10 -7-9.9 × 10-7 S cm-1 at 300°C. Magnetic measurements reveal that there are very weak antiferromagnetic interactions among the metal centers of the three compounds. Crystal data: MnBPO-CJ25, hexagonal, P63/m (No. 176), a = 11.9683(5) Å, c = 12.1303(6) Å, and Z = 2; CoBPO-CJ25, hexagonal, P63/m (No. 176), a = 11.7691(15) Å, c = 12.112(2) Å, and Z = 2; NiBPO-CJ25, hexagonal, P63/m (No. 176), a = 11.7171(5) Å, c = 12.0759(7) Å, and Z = 2.
UR - http://www.scopus.com/inward/record.url?scp=33646413932&partnerID=8YFLogxK
U2 - 10.1021/ic051916f
DO - 10.1021/ic051916f
M3 - Article
AN - SCOPUS:33646413932
SN - 0020-1669
VL - 45
SP - 3588
EP - 3593
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 9
ER -