Electrochemical functions of metallosupramolecular nanomaterials
Electrochemical functions of metallosupramolecular nanomaterials
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DOI：
10.1002/tcr.20118
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发表时间：
2007-01-01
期刊：
影响因子：
6.6
通讯作者：
Kurth, Dirk G.
中科院分区：
文献类型：
--
作者：
Higuchi, Masayoshi;Kurth, Dirk G.
金属离子和有机配体的自组装导致形成延伸或离散的金属超分子结构。在中性双位配体如双吡啶的情况下，形成扩展金属超分子配位聚电解质（MEPEs）。金属离子诱导1,4-二（2,2':6',2"-三吡啶-4'-基）苯与Fe（II）或Co（II）的自组装产生具有有趣电化学性能的mepe。这些mepe在氧化或还原时可逆地改变其颜色。由Fe（II）和Co（II）组成的异金属MEPE结合了单个MEPE的性质，因此呈现出不同的状态：红紫色、蓝色和透明。另一方面，环苯基甲胺与金属离子络合形成离散的金属超分子结构。我们发现，由于亚胺构象的碱度不同，金属离子组装到有机模块的过程是逐步发生的，金属离子组装可以通过电化学控制：这个例子说明了金属离子结合是如何通过受体的构象来控制的，这是以可预测的方式组装有机配体和金属离子的重要一步。(c) 2007日本化学期刊论坛和Wiley期刊公司。化学通报7:203-209；2007年：发表于Wiley InterScience网站。
Self-assembly of metal ions and organic ligands results in the formation of extended or discrete metallosupramolecular structures. In case of neutral ditopic ligands such as bisterpyridines, extended metallosupramolecular coordination polyelectrolytes (MEPEs) are formed. Metal ion-induced self-assembly of 1,4-bis(2,2':6',2"-terpyridin-4'-yl) benzene with Fe(II) or Co(II) results in MEPEs with interesting electrochemical properties. These MEPEs reversibly change their color when oxidized or reduced. The heterometallic MEPE consisting of Fe(II) and Co(II) combines the properties of the individual MEPEs and therefore shows their different states: red-purple, blue, and transparent. On the other hand, complexation of cyclic phenylazomethines with metal ions results in discrete metallosupramolecular structures. We find that metal ion assembly to the organic module occurs in a stepwise fashion because of a difference in the basicity of the imine conformers, and the metal ion assembly can be controlled electrochemically: This example illustrates how metal ion binding can be controlled by the conformation of the receptor, an important step toward assembling organic ligands and metal ions in predictable ways. (c) 2007 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Chem Rec 7: 203-209; 2007: Published online in Wiley InterScience.