State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, 350002, PR China.
Dalton Trans. 2010 Feb 14;39(6):1473-9. doi: 10.1039/b917907k. Epub 2009 Dec 3.
Systematic explorations of new phases in the Ag(I)-Ti(IV)/V(V)/Mo(VI)-iodate systems led to four new quaternary silver iodates, namely, Ag(2)Ti(IO(3))(6), Ag(2)(VO(2))(IO(3))(3), Ag(2)(V(2)O(4))(IO(3))(4), and Ag(2)(MoO(2))(IO(3))(4). They represent the first examples of silver iodates containing d(0) transition metal cations. Ag(2)Ti(IO(3))(6) is isostructural with K(2)Ti(IO(3))(6) and its structure features a zero-dimensional (0D) Ti(IO(3))(6) anionic unit composed of non-distorted TiO(6) octahedron corner-sharing with six IO(3)(-) groups. Such anions are further bridged by Ag(+) ions into a 3D network. In both Ag(2)(VO(2))(IO(3))(3) and Ag(2)(V(2)O(4))(IO(3))(4), each vanadium(v) is octahedrally coordinated by one terminal and two bridging oxo anions as well as three iodate anions in unidentate fashion. Neighboring VO(6) octahedra form a 1D vanadium(v) oxide chain via corner-sharing oxo anions, such chains are further decorated by iodate anions in bridging or unidentate fashion. Ag(2)(VO(2))(IO(3))(3) features a thick triple layer composed of two Ag(2)(VO(2))(IO(3))(2) and one Ag(1)IO(3) sheet whereas Ag(2)(V(2)O(4))(IO(3))(4) features a 3D network composed of 1D (V(2)O(4))(IO(3))(3) anionic chains along the c-axis that are interconnected by Ag(4)(IO(3))(2) clusters. Ag(2)(MoO(2))(IO(3))(4) is isostructural with K(2)(MoO(2))(IO(3))(4) and its structure features a 3D network built from 0D (MoO(2))(IO(3))(4) anions further interconnected by Ag(+) ions. Optical and luminescent property measurements as well as band structure calculations based on density functional theory (DFT) methods have also been performed.
系统地探索了 Ag(I)-Ti(IV)/V(V)/Mo(VI)-碘酸盐体系中的新相，得到了四个新的四元银碘酸盐，分别为 Ag(2)Ti(IO(3))(6)、Ag(2)(VO(2))(IO(3))(3)、Ag(2)(V(2)O(4))(IO(3))(4)和 Ag(2)(MoO(2))(IO(3))(4)。它们代表了含有 d(0)过渡金属阳离子的银碘酸盐的首例。Ag(2)Ti(IO(3))(6)与 K(2)Ti(IO(3))(6)同构，其结构特征为零维（0D）Ti(IO(3))(6)阴离子单元，由非扭曲的 TiO(6)八面体通过与六个 IO(3)(-)基团共享角连接而成。这些阴离子进一步通过 Ag(+)离子桥接形成 3D 网络。在 Ag(2)(VO(2))(IO(3))(3)和 Ag(2)(V(2)O(4))(IO(3))(4)中，每个钒(V)均以五配位的方式与一个末端和两个桥接氧阴离子以及三个碘酸根阴离子配位，形成单齿配位。相邻的 VO(6)八面体通过共享角的氧阴离子形成一维钒(V)氧化物链，这些链通过桥接或单齿配位的方式进一步用碘酸根阴离子修饰。Ag(2)(VO(2))(IO(3))(3)具有由两个 Ag(2)(VO(2))(IO(3))(2)和一个 Ag(1)IO(3)片组成的厚的三层结构，而 Ag(2)(V(2)O(4))(IO(3))(4)具有由沿 c 轴的一维(V(2)O(4))(IO(3))(3)阴离子链组成的 3D 网络，这些链通过Ag(4)(IO(3))(2)簇相互连接。Ag(2)(MoO(2))(IO(3))(4)与 K(2)(MoO(2))(IO(3))(4)同构，其结构特征为 3D 网络，由 0D(MoO(2))(IO(3))(4)阴离子进一步通过 Ag(+)离子相互连接而成。还进行了基于密度泛函理论（DFT）方法的光学和发光性质测量以及能带结构计算。
