Yang Miao, Yu Jihong, Di Jiancheng, Li Jiyang, Chen Peng, Fang Qianrong, Chen Yan, Xu Ruren
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012, P.R. China.
Inorg Chem. 2006 May 1;45(9):3588-93. doi: 10.1021/ic051916f.
Three new open-framework transition-metal borophosphates Na5(H3O){M(II)3[B3O3(OH)]3(PO4)6}.2H2O (M(II) = 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 [M(II)(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 PO4 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 degrees 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 x 10(-7)-9.9 x 10(-7) S cm(-1) at 300 degrees C. Magnetic measurements reveal that there are very weak antiferromagnetic interactions among the metal centers of the three compounds. Crystal data: MnBPO-CJ25, hexagonal, P6(3)/m (No. 176), a = 11.9683(5) A, c = 12.1303(6) A, and Z = 2; CoBPO-CJ25, hexagonal, P6(3)/m (No. 176), a = 11.7691(15) A, c = 12.112(2) A, and Z = 2; NiBPO-CJ25, hexagonal, P6(3)/m (No. 176), a = 11.7171(5) A, c = 12.0759(7) A, and Z = 2.
在温和水热条件下合成了三种新型的开放框架过渡金属硼磷酸盐Na5(H3O){M(II)3[B3O3(OH)]3(PO4)6}.2H2O（M(II)=Mn、Co、Ni）（记为MBPO-CJ25）。单晶X射线衍射分析表明，这三种化合物具有同构的三维（3D）开放框架，沿[001]方向有一维12元环通道。值得注意的是，该结构也可视为由具有Kagomé拓扑结构的金属磷酸盐层[M(II)(PO4)2]4-组成，这些层通过[B3O7(OH)]三硼酸盐进一步连接，形成三维开放框架。客体水分子位于12元环通道中。部分Na+离子位于12元环通道壁内的10元环侧袋中，其他Na+离子和质子化水分子位于由MO6和PO4多面体界定的6元环窗口中，以补偿阴离子框架的负电荷。这些化合物具有较高的热稳定性，在约500℃煅烧时稳定。测量了这三种化合物由于Na+离子移动而产生的离子电导率。它们在300℃时具有相似的1.13 - 1.25 eV活化能和2.7×10(-7)-9.9×10(-7) S cm(-1)的电导率。磁性测量表明，这三种化合物的金属中心之间存在非常弱的反铁磁相互作用。晶体数据：MnBPO-CJ25，六方晶系，P6(3)/m（编号176），a = 11.9683(5) Å，c = 12.1303(6) Å，Z = 2；CoBPO-CJ25，六方晶系，P6(3)/m（编号176），a = 11.7691(15) Å，c = 12.112(2) Å，Z = 2；NiBPO-CJ25，六方晶系
