Metal-complex assemblies constructed from the flexible hinge-like ligand H2bhnq: structural versatility and dynamic behavior in the solid state.
Metal-complex assemblies constructed from the flexible hinge-like ligand H2bhnq: structural versatility and dynamic behavior in the solid state.
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DOI：
10.1002/chem.200305640
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发表时间：
2004-06
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影响因子：
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通讯作者：
Koichi Yamada;Sadahiro Yagishita;Hirokazu Tanaka;Kazuhiro Tohyama;K. Adachi;S. Kaizaki;H. Kumagai
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文献类型：
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作者：
Koichi Yamada;Sadahiro Yagishita;Hirokazu Tanaka;Kazuhiro Tohyama;K. Adachi;S. Kaizaki;H. Kumagai
本文合成了由柔性铰链状配体H(2)bhnq (H（2)bhnq=2,2′-双（3-羟基-1,4-萘醌））构成的新型金属配合物。这些化合物的x射线晶体结构表明，金属离子的变化可获得四种类型的结构。在铜（II）化合物1-3中，螯合的bhnq（2-）离子桥接铜（II）中心形成一维之字形链。1-3链通过氢键相互作用和堆叠相互作用排列形成多孔结构。钴（II）和锌（II）化合物4和5形成一维螺旋链。在图4和图5中，晶体填充诱导螺旋链的自发分解，形成垂直于螺旋的手性空腔。镍（II）化合物6和7形成环四聚体。第四种结构是二聚体（化合物8），由锌（II）和bhnq（2-）在甲醇中反应得到。在这些化合物中，bhnq（2-）离子的二面角和金属配位模式的变化诱导了结构的多功能性。铜（II）化合物之字形链的组合表现出可逆的气相变色行为。UV/Vis，粉末x射线衍射，EPR和吸附等温线测量表明，这种气相变色行为是基于bhnq（2-）离子的铰链样柔韧性。
Novel metal-complex assemblies constructed from the flexible hinge-like ligand H(2)bhnq (H(2)bhnq=2,2'-bi(3-hydroxy-1,4-naphthoquinone)) have been synthesized. The X-ray crystal structures of these compounds reveal that four types of architectures are accessible by variation of the metal ions. In copper(II) compounds 1-3, the chelating bhnq(2-) ions bridge copper(II) centers to form one-dimensional zigzag chains. The chains of 1-3 are arranged by hydrogen-bonding interactions and stacking interactions to produce porous structures. Cobalt(II) and zinc(II) compounds 4 and 5 form one-dimensional helical chains. In 4 and 5, the crystal packing induces spontaneous resolution of the helical chains with chiral cavities formed perpendicular to the helices. Nickel(II) compounds 6 and 7 form cyclic tetramers. The fourth architecture, a dimer (compound 8), is obtained by the reaction of zinc(II) and bhnq(2-) in MeOH. In these compounds, changes of the dihedral angles and the metal-coordination mode of the bhnq(2-) ion induce the structural versatility. The assemblies of the zigzag chains of the copper(II) compounds exhibit reversible vapochromic behavior. UV/Vis, powder X-ray diffraction, EPR, and adsorption isotherm measurements indicate that this vapochromic behavior is based on the hinge-like flexibility of the bhnq(2-) ion.