Metal nuclearity modulated four-, six-, and eight-connected entangled frameworks based on mono-, bi-, and trimetallic cores as nodes.
Metal nuclearity modulated four-, six-, and eight-connected entangled frameworks based on mono-, bi-, and trimetallic cores as nodes.
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DOI：
10.1002/chem.200501242
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发表时间：
2006-03
期刊：
影响因子：
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通讯作者：
Xinlong Wang;C. Qin;E. Wang;Z. Su
中科院分区：
文献类型：
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作者：
Xinlong Wang;C. Qin;E. Wang;Z. Su
为了研究网络连连性与金属核性之间的关系，我们设计并合成了一系列基于不同金属核的三维（3D）缠结配位框架，即[Zn(2)(bdc)(2)(L)(2)]2H(2)O (1), [Zn(bdc)(L)(0.5)] (2), [Zn(oba)(L)(0.5)](3)和[Cd(3)(bdc)(3)(L)(2)(H(2)O)(4)](4)。以及刚性和非刚性芳香二羧酸配体1,4-苯二羧酸酯（bdc）和4,4'-氧双（苯甲酸酯）（oba）。化合物1在单一Zn中心具有典型的基于四面体第二构建单元（SBU）的三重互穿金刚石阵列。化合物2采用由双金属芯作为6个连接顶点构建的三重互穿α -钋型网络。3的结构也由双核单位组成；它包括一种新颖的（3,4）连接的三重互穿网，当单锌中心作为四连接节点时，具有复杂的（4610）（46(2)）（10(3)）拓扑结构（或者如果将双核单元视为六连接节点则为α - po拓扑结构）。化合物4源自交联的五重互穿类金刚石子结构，是一种不寻常的自穿透配位框架，具有前所未有的8连接4(20)6(8)拓扑结构，三核镉簇作为8连接节点，据我们所知，这不仅定义了8连接配位网络的新拓扑结构，而且代表了目前已知的自穿透系统的最高连接拓扑结构。这些配合物的详细结构比较表明，金属核的增加导致最终网络的连通性逐渐增加，即金属核在调节特定网络的连通性方面起着重要作用。讨论了这些化合物的热性能和发光性能。
To investigate the relationship between network connectivity and metal nuclearity, we designed and synthesized a series of three-dimensional (3D) entangled coordination frameworks based on different metal cores, namely [Zn(2)(bdc)(2)(L)(2)]2H(2)O (1), [Zn(bdc)(L)(0.5)] (2), [Zn(oba)(L)(0.5)] (3) and [Cd(3)(bdc)(3)(L)(2)(H(2)O)(2)] (4) by self-assembly of d(10) metal salts with the flexible long-chain ligand 1,4-bis(1,2,4-triazol-1-yl)butane (L), and with the rigid and nonrigid aromatic dicarboxylate ligands 1,4-benzenedicarboxylate (bdc) and 4,4'-oxybis(benzoate) (oba). Compound 1 exhibits a threefold interpenetrated diamondoid array typically based on a tetrahedral second building unit (SBU) at a single Zn center. Compound 2 adopts a threefold interpenetrated alpha-polonium-type network that is built from bimetallic cores as six-connected vertices. The structure of 3 also consists of dinuclear units; it comprises a novel (3,4)-connected threefold interpenetrated net with complex (4610)(46(2)10(3)) topology when single zinc centers act as four-connected nodes (or the alpha-Po topology if dinuclear units are considered as six-connected nodes). Compound 4, derived from a crosslinked fivefold interpenetrated diamond-like substructure, is an unusual example of a self-penetrating coordination framework displaying an unprecedented eight-connected 4(20)6(8) topology with trinuclear cadmium clusters as eight-connected nodes which, to our knowledge, not only defines a new topology for eight-connected coordination networks, but also represents the highest connected topology presently known for self-penetrating systems. Detailed structural comparison of these complexes indicates that the increase in metal nuclearity induces the progressive increase in the connectivities of the ultimate nets: that is, the metal nuclearity plays a significant role in tuning the connectivity of a specific network. The thermal and luminescent properties of these compounds are discussed.