Department of Materials Science and Engineering, College of Materials, Xiamen University, Xiamen 361005, China.
Inorg Chem. 2013 Aug 19;52(16):9169-71. doi: 10.1021/ic401329d. Epub 2013 Aug 8.
Structural assembly from phosphate to germanophosphate by applying germanate as a binder has been achieved. Two isotypic porous compounds, K3[M(II)4(HPO4)2][Ge2O(OH)(PO4)4]·xH2O (M(II) = Fe, Cd; x = 2 for Fe and 3 for Cd, denoted as KFeGePO-1 and KCdGePO-1, respectively), contain a known transition-metal phosphate (TMPO) layer, (∞)(2){[M2(HPO4)3]2–}, which is built from chains of trans-edge-sharing MO6 octahedra bridged by MO5 trigonal bipyramids that were further linked and decorated by phosphate tetrahedra. The layers are bound by infinite chains of GeO5(OH) octahedra, resulting in a 3D open-framework structure with 1D 12-ring channels that are occupied by K+ ions and water molecules. The curvature of the TMPO layers and shape of the 12-ring windows can be tuned by the transition metals because of their Jahn–Teller effect.
通过应用锗酸盐作为粘结剂，已经实现了从磷酸盐到锗磷酸盐的结构组装。两种同构多孔化合物，K3[M(II)4(HPO4)2][Ge2O(OH)(PO4)4]·xH2O（M(II) = Fe、Cd；x = 2 对应 Fe，x = 3 对应 Cd，分别表示为 KFeGePO-1 和 KCdGePO-1），包含一个已知的过渡金属磷酸盐（TMPO）层，（∞）（2）{[M2(HPO4)3]2–}，它由由 MO5 三角双锥桥接的反平行共享 MO6 八面体链组成，进一步由磷酸盐四面体连接和修饰。这些层由无限的 GeO5(OH) 八面体链结合在一起，形成一个具有一维 12 元环通道的三维开放式骨架结构，这些通道被 K+离子和水分子占据。由于 Jahn–Teller 效应，TMPO 层的曲率和 12 元环窗口的形状可以通过过渡金属来调节。
