The solid-state architecture of a metallosupramolecular polyelectrolyte
The solid-state architecture of a metallosupramolecular polyelectrolyte
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DOI：
10.1073/pnas.0601092103
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发表时间：
2006-07
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影响因子：
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通讯作者：
U. Kolb;K. Büscher;C. Helm;A. Lindner;A. Thünemann;M. Menzel;M. Higuchi;D. Kurth
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文献类型：
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作者：
U. Kolb;K. Büscher;C. Helm;A. Lindner;A. Thünemann;M. Menzel;M. Higuchi;D. Kurth
铁（II）和双配体1,4-二（2,2 ':6 ‘，2″-三吡啶-4 ’ -酰基）苯的自组装在溶液中产生平衡结构，即所谓的金属超分子配位聚电解质（MEPEs）。由于这种大分子的动态性质，对其进行表征是极其困难的。因此，几乎没有任何结构信息可用于这种类型的材料。在这里，我们表明，在小聚集体占主导地位的稀溶液中，有可能在界面上生长纳米级晶体。利用电子衍射和分子模拟相结合的方法研究了MEPE的纳米晶体，获得了近原子分辨率的结构。分析结果显示为原始单斜胞（P21/c空间群，a = 10.4 Å， b = 10.7 Å， c = 34.0 Å， α = γ = 90°，β = 95°，ρ = 1.26 g/cm3, Z = 4）。MEPE形成线状棒，这些线状棒被组织成片状。四个薄片与单元格相交，而相邻的薄片相互旋转90°。通过Mössbauer光谱分析证实了Fe（II）中心的伪八面体配位几何。本文提出的衍射和分子模型的结合可能对解决结构材料科学中的问题具有普遍的实用价值。
Self-assembly of Fe(II) and the ditopic ligand 1,4-bis(2,2′:6′,2″-terpyridine-4′-yl)benzene results in equilibrium structures in solutions, so-called metallosupramolecular coordination polyelectrolytes (MEPEs). It is exceedingly difficult to characterize such macromolecular assemblies, because of the dynamic nature. Therefore, hardly any structural information is available for this type of material. Here, we show that from dilute solutions, where small aggregates predominate, it is possible to grow nanoscopic crystals at an interface. A near atomic resolution structure of MEPE is obtained by investigating the nanoscopic crystals with electron diffraction in combination with molecular modeling. The analysis reveals a primitive monoclinic unit cell (P21/c space group, a = 10.4 Å, b = 10.7 Å, c = 34.0 Å, α = γ = 90°, β = 95°, ρ = 1.26 g/cm3, and Z = 4). The MEPE forms linear rods, which are organized into sheets. Four sheets intersect the unit cell, while adjacent sheets are rotated by 90° with respect to each other. The pseudooctahedral coordination geometry of the Fe(II) centers is confirmed by Mössbauer spectroscopy. The combination of diffraction and molecular modeling presented here may be of general utility to address problems in structural materials science.