A springlike 3D-coordination network that shrinks or swells in a crystal-to-crystal manner upon guest removal or readsorption
A springlike 3D-coordination network that shrinks or swells in a crystal-to-crystal manner upon guest removal or readsorption
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DOI：
10.1002/1521-3773(20020916)41:18
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发表时间：
2002-01-01
影响因子：
16.6
通讯作者：
Fujita, M
中科院分区：
文献类型：
--
作者：
Biradha, K;Fujita, M
本文的支持信息可在WWW上的http：//www. angewandte。org或作者。收敛金属中心。[5]同时，在配位聚合物中，Robson及其同事表明，配体1可以在与过渡金属反应时自组装成3D网络。[6]我们在这里报告了由1和ZnI 2组装的双重互穿的（10，3）-B网络的前所未有的动态性质：也就是说，当客体分子被移除时，它会收缩，当它们返回时，它会膨胀（图1），而不会破坏晶体性质。[7]此外，我们发现，客体分子可以控制形成相同的（10，3）-B构型的双互穿和非互穿网络。Batten和Robson公开了1与ZnCl 2形成类似类型的双重互穿网络。[8]将ZnI 2的MeOH溶液扩散到1的硝基苯/MeOH溶液中，得到了配合物[{（ZnI 2）3（1）2¥ 6 C6 H5 NO2} n]（2）的单晶。单晶分析的复杂揭示了一个双互穿的三维网络的形成。[9]在2的晶体结构中，Znatoms采用四面体几何形状，因为I原子和TPT的吡啶部分各自占据两个位点。3D网络中的最短电路包含10个1分子和10个Zn原子（图2a），并且如果Zn原子被认为是间隔物并且1的部分被认为是三个连接的节点，则网络可以被分类为具有（10，3）-B构型。沿着（010）轴，网络可以被认为是一个螺旋形的六边形3D网络，节距长度为15（图2 B）。[10]这些网中的两个相互渗透，从而存在连续的通道（图2c，d）。尽管网络相互连接，但60%的晶胞体积被硝基苯分子占据，硝基苯分子部分无序。有趣的是，网络的相互渗透不会干扰通道的形成，因为通道的方向与两个网络的方向重叠（图2d）。用苯甲腈代替硝基苯也得到类似的配合物[{（ZnI 2）3（1）2¥ 6 C6 H5 CN} n]（3）。[第十一届]
Supporting information for this article is available on the WWW under http://www. angewandte. org or from the author. convergent metal centers.[5] Simultaneously, in coordination polymers, Robson and co-workers showed that ligand 1 can self-assemble into 3D networks upon reaction with transition metals.[6] We report here the unprecedented dynamic nature of a doubly interpenetrated (10, 3)-b network that assembles from 1 and ZnI2: that is, it shrinks when guest molecules are removed and swells when they are returned (Figure1) without destruction of the crystalline nature.[7] Furthermore, we show that guest molecules can control the formation of doubly interpenetrated and non-interpenetrated networks of the same (10, 3)-b configuration. Batten and Robson disclosed that 1 with ZnCl2 forms a similar type of doubly interpenetrated network.[8]The diffusion of a solution of ZnI2 in MeOH into a nitrobenzene/MeOH solution of 1 resulted in single crystals of the complex [{(ZnI2) 3 (1) 2¥ 6 C6H5NO2} n](2). Single-crystal analysis of the complex revealed the formation of a doubly interpenetrated 3D network.[9] In the crystal structure of 2, the Znatoms adopt a tetrahedral geometry as the I atoms and pyridine moieties of TPT occupy two sites each. The shortest circuits in the 3D network contain ten molecules of 1 and ten Zn atoms (Figure 2a) and the network can be classified as having a (10, 3)-b configuration, if the Zn atoms are considered to be spacers and the moieties of 1 to be three connected nodes. Along the (010) axis, the network can be regarded as a helical, hexagonal 3D network with a pitch length of 15ä (Figure 2 b).[10] Two of these nets are interpenetrated such that continuous channels exist (Figure 2c, d). Despite this interlinking of the networks, 60% of the unit-cell volume is occupied by the nitrobenzene molecules, which are partially disordered. Interestingly, the interpenetration of the networks does not interfere in channel formation as the channels run in a direction overlapping that of the two networks (Figure 2d). The use of cyanobenzene in place of nitrobenzene also resulted in a similar complex [{(ZnI2) 3 (1) 2¥ 6 C6H5CN} n](3).[11]