State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, People's Republic of China.
Inorg Chem. 2010 Jul 5;49(13):5943-52. doi: 10.1021/ic100462r.
Systematic explorations of the new phases in the Pb(II)/Bi(III)-TM(d(0)/d(1))-Se(IV)-O systems by hydrothermal syntheses led to five new quaternary phases whose structures are composed of three different asymmetric building units, namely, Pb(2)V(V)(2)Se(2)O(11) (1), Pb(2)V(IV)(3)Se(5)O(18) (2), Pb(2)Nb(V)(2)Se(4)O(15) (3), Bi(2)V(V)(2)Se(4)O(16) (4), and Bi(2)Mo(VI)(2)Se(2)O(13) (5). The structure of 1 features a 3D network built by 1D anionic chains of V(2)O(5)(SeO(3))(2) interconnected by Pb(2+) ions with six-membered-ring (MR) tunnels along the b axis. The structure of 2 features a 3D anionic framework composed of V(IV)O(6) octahedra corner-sharing with SeO(3) anions, with the Pb(2+) ions located at the resultant 8-MR tunnels. The oxidation state of the vanadium cation is 4+ due to the partial oxidation of V(2)O(3) by SeO(2) at high temperature. The structure of 3 features novel 1D double chains of Nb(2)O(3)(SeO(3))(4) that are interconnected by Pb(2+) ions, forming a 3D network with 12-MR tunnels along the c axis. 4 features a 3D framework composed of 2D layers of Bi(2)(SeO(3))(2) and 1D (VO(2))(2)(SeO(3))(2) double chains. The structure of 5 features a 3D network composed of bismuth(III) selenite with large 10-MR tunnels along the a axis that are occupied by Mo(2)O(10) dimers. The results of optical diffuse-reflectance spectrum measurements and electronic structure calculations based on density functional theory methods indicate that all five compounds are wide-band-gap semiconductors. Luminescent property measurements for compounds 1-5 and magnetic measurements for compound 2 were also made.
通过水热合成方法对 Pb(II)/Bi(III)-TM(d(0)/d(1))-Se(IV)-O 体系中的新相进行系统探索，得到了五个新的四元相，它们的结构由三个不同的不对称构建单元组成，分别是 Pb(2)V(V)(2)Se(2)O(11) (1)、Pb(2)V(IV)(3)Se(5)O(18) (2)、Pb(2)Nb(V)(2)Se(4)O(15) (3)、Bi(2)V(V)(2)Se(4)O(16) (4) 和 Bi(2)Mo(VI)(2)Se(2)O(13) (5)。1 的结构特点是由一维阴离子链V(2)O(5)(SeO(3))(2)组成的 3D 网络，该链通过 Pb(2+)离子相互连接，沿 b 轴具有六元环（MR）隧道。2 的结构特点是由 V(IV)O(6)八面体与 SeO(3)阴离子共角构成的 3D 阴离子骨架，Pb(2+)离子位于生成的 8-MR 隧道中。由于高温下 SeO(2)对 V(2)O(3)的部分氧化，钒阳离子的氧化态为 4+。3 的结构特点是新型的Nb(2)O(3)(SeO(3))(4)一维双链，通过 Pb(2+)离子相互连接，形成沿 c 轴具有 12-MR 隧道的 3D 网络。4 的结构特点是由二维层Bi(2)(SeO(3))(2)和一维(VO(2))(2)(SeO(3))(2)双链组成的 3D 骨架。5 的结构特点是由铋(III)亚硒酸盐组成的 3D 网络，沿 a 轴具有大的 10-MR 隧道，由 Mo(2)O(10)二聚体占据。基于密度泛函理论方法的光学漫反射光谱测量和电子结构计算结果表明，这五个化合物都是宽带隙半导体。还对化合物 1-5 进行了发光性能测量，对化合物 2 进行了磁性测量。
