Ternary nets formed by self-assembly of triangles, squares, and tetrahedra.
Ternary nets formed by self-assembly of triangles, squares, and tetrahedra.
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DOI：
10.1002/anie.200500156
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发表时间：
2005-05
影响因子：
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通讯作者：
Zhenqiang Wang;V. Kravtsov;M. Zaworotko
中科院分区：
文献类型：
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作者：
Zhenqiang Wang;V. Kravtsov;M. Zaworotko
自从威尔斯将晶体中的网络结构编入目录以来，已经过去了近30年，他的方法促进了晶体工程[2]的广泛的无限二维和三维网络。晶体工程网络调用几何设计原理意味着化学上多样化的分子构建块（MBB）可用于研究，例如配位聚合物（即金属有机网络），[3]由有机金属键支撑的聚合物[4]和氢键有机网络。[5]配位聚合物是特别有吸引力的研究目标：金属配位和簇几何形状多种多样，但它们是可控的，有助于设计具有可预测拓扑结构和尺寸的网络;金属部分可以预先选择，以赋予功能特性，如磁性，[6]发光[7]，或者在开放框架网络的情况下，永久多孔性;[3c，e，8]多官能有机配体也可以根据它们的几何属性进行选择。配位聚合物可以使用“节点和间隔物”方法合理化和设计，[3a，B]该方法将分子构建块简化为拓扑点和线。近年来分离出的美观且具有潜在功能的配位聚合物的例子有（10，3）-a，[9] NbO，[10]金刚烷，[11]和原始立方网。[12]另一种用于解释和设计网的策略考虑了MBB的形状，并将网表示为由顶点连接的多边形或多面体（VLPP）维持。[6a，13]如Scheme 1所揭示的，上述四种网络类型可以被视为“节点和间隔器”或VLPP网络。从VLPP的角度来看，方案1中所示的四个网都是单一网的示例，因为它们完全由一种类型的多边形或多面体构建。VLPP方法适用于二元网络，即由多边形或多面体MBB对支撑的网络。甚至最简单的MBB也可能具有结构多样性，例如（3，4）-连通网。如果正方形只连接到三角形，反之亦然，两个不同的（3，4）连接的二元网络已经被隔离：Pt 3 O 4 [14]和扭曲的硼酸盐网络。[13a同样地，如果四面体只与三角形相连，反之亦然，则可以访问两个额外的（3，4）-连接的二元网，即方铅矿[16]和立方C3 N4网[17]（方案2）。在这里，我们解决如何VLPP的方法可以扩展到三元网，也就是说，那些由三个多边形或多面体的组合。我们报告了两种化合物的合成和晶体结构，这两种化合物代表由三种不同的MBB维持的三元VLPP网络的原型实例：[{[Zn 6（btc）4（异喹啉）6（MeOH）] H2O（苯）2} n]（USF-3; btc= 1，3，5-苯三羧酸酯）和[{[Zn 6-（btc）4（异喹啉）4（MeOH）2]（MeOH）8（氯苯）} n]（USF-4）。USF-3和USF-4是由三角形、正方形和四面体MBB的顶点连接维持的，据我们所知，它们是第一个报道的三元网的例子。的
It has now been almost thirty years since Wells catalogued network structures in crystals [1] in a manner that has facilitated the crystal engineering [2] of a wide range of infinite 2D and 3D nets. That crystal engineered nets invoke geometric design principles means that a chemically diverse range of molecular building blocks (MBBs) are available for study as exemplified by coordination polymers (ie metal–organic networks),[3] polymers sustained by organometallic linkages [4] and hydrogen-bonded organic networks.[5] Coordination polymers are particularly attractive targets for study: metal coordination and cluster geometries are diverse but they are controllable in a manner that facilitates the design of nets with predictable topology and dimensions; metal moieties can be pre-selected so as to impart functional properties, such as magnetism,[6] luminescence [7] or, in the case of openframework nets, permanent porosity;[3c, e, 8] multifunctional organic ligands can also be selected for their geometric attributes. Coordination polymers can be rationalized and designed using the “node-and-spacer” approach,[3a, b] which simplifies molecular building blocks into topological points and lines. Aesthetically pleasing and potentially functional coordination polymers that have been isolated in recent years are exemplified by (10, 3)-a,[9] NbO,[10] diamondoid,[11] and primitive cubic nets.[12] An alternative strategy for the interpretation and design of nets takes into account the shape of the MBBs and represents nets as being sustained by vertex-linked polygons or polyhedra (VLPP).[6a, 13] As revealed by Scheme1, the aforementioned four net types can be visualized as being either “node-and-spacer” or VLPP networks. From the VLPP perspective, the four nets shown in Scheme 1 are all examples of unitary nets in that they are built entirely from one type of polygon or polyhedron. The VLPP approach comes into its own for binary nets, that is, nets sustained by pairs of polygonal or polyhedral MBBs. The structural diversity possible from even the simplest of MBBs is exemplified by (3, 4)-connected nets. If squares are connected exclusively to triangles and vice versa, two distinct (3, 4)-connected binary nets have been isolated: the Pt3O4[14] and twisted boracite nets.[13a, 15] Likewise, if tetrahedra are linked exclusively to triangles and vice versa, two additional (3, 4)-connected binary nets are accessible, the boracite [16] and cubic C3N4 nets [17](Scheme 2). Herein we address how the VLPP approach can be extended to ternary nets, that is, those sustained by a combination of three polygons or polyhedra. We report the synthesis and crystal structures of two compounds that represent prototypal examples of ternary VLPP nets sustained by three distinct MBBs:[{[Zn6 (btc) 4 (isoquinoline) 6 (MeOH)] H2O (benzene) 2} n](USF-3; btc= 1, 3, 5-benzenetricarboxylate), and[{[Zn6-(btc) 4 (isoquinoline) 4 (MeOH) 2](MeOH) 8 (chlorobenzene)} n](USF-4). USF-3 and USF-4 are sustained by vertex linkage of triangular, square, and tetrahedral MBBs and represent to our knowledge the first reported examples of ternary nets. The