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 Dec 20;49(24):11573-80. doi: 10.1021/ic101843g. Epub 2010 Nov 15.
Systematic explorations of new compounds in the Li(I)-Ga(III)-Te(IV)-O system led to two new isomeric ternary gallium tellurites, namely, α-Ga(2)(TeO(3))(3) and β-Ga(2)(TeO(3))(3), and two new quaternary lithium gallium tellurites, namely, HLi(2)Ga(3)(TeO(3))(6)(H(2)O)(6) and Li(9)Ga(13)Te(21)O(66). α-Ga(2)(TeO(3))(3) is a noncentrosymmetric structure (I4̅3d) and displays a moderately strong second-harmonic-generation response that is comparable with that of KDP (KH(2)PO(4)). Its structure features a condensed three-dimensional (3D) network alternatively connected by GaO(4) tetrahedra and TeO(3) trigonal pyramids via corner sharing. β-Ga(2)(TeO(3))(3) is centrosymmetric (P6(3)/m) and features a 3D open framework composed of Ga(2)O(9) dimers bridged by TeO(3) groups with one-dimensional (1D) 12-MR channels along the c axis. Although both HLi(2)Ga(3)(TeO(3))(6)(H(2)O)(6) and Li(9)Ga(13)Te(21)O(66) crystallized in the same space group R3̅, they belong to different structure types. The structure of HLi(2)Ga(3)(TeO(3))(6)(H(2)O)(6) can be viewed as the 1D tunnels of the 3D gallium tellurite being occupied by Li(+) and H(+) ions whereas the structure of Li(9)Ga(13)Te(21)O(66) is a complicated 3D framework composed of alternating gallium tellurite layers and GaO(6) octahedral layers with Li(+) cations being located at the cavities of the structure. Optical diffuse-reflectance spectrum measurements indicate that all four compounds are insulators and transparent in the range of 300-2500 nm.
在 Li(I)-Ga(III)-Te(IV)-O 体系中对新化合物的系统探索导致了两种新的同构三价镓碲酸盐，即 α-Ga(2)(TeO(3))(3)和β-Ga(2)(TeO(3))(3)，以及两种新的四元锂镓碲酸盐，即 HLi(2)Ga(3)(TeO(3))(6)(H(2)O)(6)和 Li(9)Ga(13)Te(21)O(66)。α-Ga(2)(TeO(3))(3)是一个非中心对称结构（I4̅3d），表现出与 KDP（KH(2)PO(4)）相当的中等强度的二次谐波产生响应。它的结构特征是通过角共享由 GaO(4)四面体和 TeO(3)三角锥交替连接的凝聚三维（3D）网络。β-Ga(2)(TeO(3))(3)是中心对称的（P6(3)/m），具有由 TeO(3)基团桥接的 Ga(2)O(9)二聚体组成的 3D 开放骨架，沿 c 轴具有一维（1D）12-MR 通道。尽管 HLi(2)Ga(3)(TeO(3))(6)(H(2)O)(6)和 Li(9)Ga(13)Te(21)O(66)都在相同的空间群 R3̅中结晶，但它们属于不同的结构类型。HLi(2)Ga(3)(TeO(3))(6)(H(2)O)(6)的结构可以看作是三维镓碲酸盐的一维隧道被 Li(+)和 H(+)离子占据，而 Li(9)Ga(13)Te(21)O(66)的结构是由交替的镓碲酸盐层和 GaO(6)八面体层组成的复杂 3D 骨架，Li(+)阳离子位于结构的空腔中。光学漫反射光谱测量表明，所有四种化合物在 300-2500nm 范围内都是绝缘体和透明的。
