Assembly of discrete, one-, two-, and three-dimensional silver(I) supramolecular complexes containing encapsulated acetylide dianion with nitrogen-donor spacers.
Assembly of discrete, one-, two-, and three-dimensional silver(I) supramolecular complexes containing encapsulated acetylide dianion with nitrogen-donor spacers.
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DOI：
10.1021/ic026019f
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发表时间：
2003-02
影响因子：
4.6
通讯作者：
Quan‐Ming Wang;T. Mak
中科院分区：
文献类型：
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作者：
Quan‐Ming Wang;T. Mak
首次成功地将双功能脱齿配体引入到乙炔基银体系中，构建了超分子结构。通过配位组装得到了5种不同的超分子配合物，分别为[（Ag（2）C（2））（AgCF（3）CO（2））（4）（pyz）（2）]（n）（1），[（Ag（2）C（2））（2）（AgCF（3）CO（2））（10）（CF（3）CO（2））（4）（DabcoH）（4）（H（2）O）[（Ag（2）C（2））（AgCF（3）CO（2））（4）（CF（3）CO（2））（bpaH）]（n）（）（3），[（Ag（2）C（2））（AgCF（3）CO（2））（8）（bpa）（4）]（n）（4），和[（Ag（2）C（2））（2）（AgCF（3）CO（2））（10）（bppz）（2）（H（2）O）]（n）（5）（pyz =吡嗪; Dabco = 1，4-二氮杂双环[2.2.2]辛烷; bpa = 1，2-双（4-吡啶基）乙烷; bppz = 2，3-双（2-吡啶基）吡嗪）。配合物1是由吡嗪桥交联的银柱组成的三维框架，而2包含一个离散的超分子，其核心是Ag（14）双笼，完全被三氟乙酸盐、水和末端单质子化的Dabco配体包围。配合物3具有树枝状结构，bpa配体的一端连接到银骨架上，另一端暴露并质子化。在4中，中性十核[（Ag（2）C（2））（AgCF（3）CO（2））（8）]单元通过bpa间隔基采用逆构象和逆构象连接，产生层状结构。另一个二维网络是以bppz为角桥联配体形成的，其中结构单元是含有24个银原子的银四重笼。
The first successful attempt to construct supramolecular entities via incorporation of bifunctional exodentate ligands into the silver acetylide system is reported. Coordination assembly with nitrogen-donor spacers led to the formation of five distinct supramolecular complexes, namely [(Ag(2)C(2))(AgCF(3)CO(2))(4)(pyz)(2)](n) (1), [(Ag(2)C(2))(2)(AgCF(3)CO(2))(10)(CF(3)CO(2))(4)(DabcoH)(4)(H(2)O)(1.5)].H(2)O (2), [(Ag(2)C(2))(AgCF(3)CO(2))(4)(CF(3)CO(2))(bpaH)](n)() (3), [(Ag(2)C(2))(AgCF(3)CO(2))(8)(bpa)(4)](n) (4), and [(Ag(2)C(2))(2)(AgCF(3)CO(2))(10)(bppz)(2)(H(2)O)](n) (5) (pyz = pyrazine; Dabco = 1,4-diazabicyclo[2.2.2]octane; bpa = 1,2-bis(4-pyridyl)ethane; bppz = 2,3-bis(2-pyridyl)pyrazine). Complex 1 is a three-dimensional framework composed of silver columns cross-linked by pyrazine bridges, whereas 2 contains a discrete supermolecule whose core is a Ag(14) double cage that is completely surrounded by trifluoroacetate, aqua, and terminal monoprotonated Dabco ligands. Complex 3 has a branched-tree architecture with one terminal of the bpa ligand attached to the silver backbone and the other exposed and protonated. In 4, neutral decanuclear [(Ag(2)C(2))(AgCF(3)CO(2))(8)] units are interlinked by bpa spacers adopting both gauche and anti conformations to generate a layer structure. Another two-dimensional network was formed with bppz serving as an angular bridging ligand in 5, in which the building unit is a silver quadruple cage containing 24 silver atoms.