Framework Solids Laboratory, Solid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore-560012, India.
Dalton Trans. 2010 Mar 7;39(9):2263-79. doi: 10.1039/b908995k. Epub 2010 Jan 12.
Five new thiosulfate based inorganic-organic hybrid open-framework compounds have been synthesized employing mild reaction conditions. Of the five compounds, [Na(2)(H(2)O)(8)][Cd(C(10)H(8)N(2))(S(2)O(3))(2)].2H(2)O, I and [Cd(2)(C(10)H(8)N(2))(2)(HS(2)O(3))(2)(S(2)O(3))(2)][(C(10)H(9)N(2))(2)(C(10)H(8)N(2))(2)].8H(2)O, II have one-dimensional (1D) structures and [Cd(C(10)H(8)N(2))(H(2)O)(2)(S(2)O(3))].2H(2)O, III, [Cd(2)(C(10)H(8)N(2))(3)(S(2)O(3))(2)], IV and [Cd(2)(C(10)H(8)N(2))(2.5)(S(2)O(3))(2)], V have three-dimensional (3D) structures. The 1D structures are somewhat related, formed by the bonding between tetrahedral Cd centers (CdN(2)S(2)) and 4,4'-bipyridine (bpy) units. The inter-chain spaces are occupied by the hanging thiosulfate units in both the cases along with Na(H(2)O)(6) chains in I and free bpy units in II. The three 3D structures have one-dimensional cadmium thiosulfate chains linked by bpy units. Interpenetration has been observed in all the 3D structures. The 3D structures appear to be related and can be derived from fgs net. Transformation studies on the 1D compound, [Na(2)(H(2)O)(8)][Cd(C(10)H(8)N(2))(S(2)O(3))(2)].2H(2)O, I, indicated a facile formation of [Cd(C(10)H(8)N(2))(H(2)O)(2)(S(2)O(3))].2H(2)O, III. Prolonged heating of I gave rise to a 3D cadmium sulfate phase, [Cd(2)(C(10)H(8)N(2))(2)(H(2)O)(3)(SO(4))(2)].2H(2)O, VI. Compound VI has one-dimensional cadmium sulfate chains formed by six-membered rings connected by bpy units to form a 3D structure, which appears to resemble the topological arrangement of III. Transformation studies of III indicates the formation of IV and V, and at a higher temperature a new 3D cadmium sulfate, [Cd(C(10)H(8)N(2))(SO(4))], VII. Compound VII has a 4 x 4 grid cadmium sulfate layers pillared by bpy units. All the compounds were characterized by PXRD, TGA, IR and UV-visible studies. Preliminary studies on the possible use of the 3D compounds (III-VII) in heterogeneous cyanosilylation of imines appear to be promising.
已经采用温和的反应条件合成了五个新的基于硫代硫酸盐的无机-有机杂化开放式框架化合物。在这五个化合物中，[Na(2)(H(2)O)(8)][Cd(C(10)H(8)N(2))(S(2)O(3))(2)].2H(2)O，I 和 [Cd(2)(C(10)H(8)N(2))(2)(HS(2)O(3))(2)(S(2)O(3))(2)][(C(10)H(9)N(2))(2)(C(10)H(8)N(2))(2)].8H(2)O，II 具有一维（1D）结构，而 [Cd(C(10)H(8)N(2))(H(2)O)(2)(S(2)O(3))].2H(2)O，III、[Cd(2)(C(10)H(8)N(2))(3)(S(2)O(3))(2)]，IV 和 [Cd(2)(C(10)H(8)N(2))(2.5)(S(2)O(3))(2)]，V 具有三维（3D）结构。一维结构有些相关，由四面体 Cd 中心（CdN(2)S(2)) 和 4,4'-联吡啶（bpy）单元之间的键合形成。在两种情况下，沿链的空间都被悬挂的硫代硫酸盐单元占据，同时在 I 中还有 Na(H(2)O)(6)链，在 II 中则是游离的 bpy 单元。三个 3D 结构都有一维的镉硫代硫酸盐链通过 bpy 单元连接。在所有 3D 结构中都观察到了贯穿。这些 3D 结构似乎相关，可以从 fgs 网络中推导出来。对一维化合物 [Na(2)(H(2)O)(8)][Cd(C(10)H(8)N(2))(S(2)O(3))(2)].2H(2)O，I 的转化研究表明，很容易形成 [Cd(C(10)H(8)N(2))(H(2)O)(2)(S(2)O(3))].2H(2)O，III。长时间加热 I 会导致形成 3D 硫酸镉相，[Cd(2)(C(10)H(8)N(2))(2)(H(2)O)(3)(SO(4))(2)].2H(2)O，VI。化合物 VI 具有通过 bpy 单元连接的六元环形成的一维硫酸镉链，形成 3D 结构，这似乎类似于 III 的拓扑排列。III 的转化研究表明形成了 IV 和 V，在更高的温度下会形成一种新的 3D 硫酸镉，[Cd(C(10)H(8)N(2))(SO(4))]，VII。化合物 VII 具有由 bpy 单元支撑的 4 x 4 网格硫酸镉层。所有的化合物都通过 PXRD、TGA、IR 和 UV-可见研究进行了表征。对可能在异相氰硅烷基化亚胺中的 3D 化合物（III-VII）的潜在用途进行了初步研究，结果似乎很有希望。
