Torands Revisited: Metal Sequestration and Self-Assembly of Cyclo-2,9-tris-1,10-phenanthroline Hexaaza Macrocycles.
Torands Revisited: Metal Sequestration and Self-Assembly of Cyclo-2,9-tris-1,10-phenanthroline Hexaaza Macrocycles.
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DOI：
10.1002/chem.201406602
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发表时间：
2015-06
期刊：
影响因子：
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通讯作者：
M. Schwab;M. Takase;Alexey Mavrinsky;W. Pisula;Xinliang Feng;J. A. Gámez;W. Thiel;K. Mali;
中科院分区：
文献类型：
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作者：
M. Schwab;M. Takase;Alexey Mavrinsky;W. Pisula;Xinliang Feng;J. A. Gámez;W. Thiel;K. Mali;
报道了一系列新颖的环状环-2,9-三-1,10-菲罗啉大环，具有罕见的六杂腔。镍介导的山本芳基偶联是功能化1,10-苯萘啉前体环三聚化的一种通用工具。由于现在改进的可加工性，在体相中的液晶行为和分子水平上的二维自组装都可以第一次研究到一个torand系统。MALDI-TOF分析和光谱分析表明，大环对不同金属阳离子的络合具有较强的亲和性。实验结果与环-2,9-三-1,10-菲罗啉空腔及其对金属阳离子的结合模式的广泛计算研究相关。由于结合了几个有趣的特性，环形大环可能会在离子和电荷通过分子通道传输领域找到未来的应用，以及在STM条件下表面受限单层的化学传感和分子写入。
A series of novel toroidal cyclo-2,9-tris-1,10-phenanthroline macrocycles with an unusual hexaaza cavity are reported. Nickel-mediated Yamamoto aryl-aryl coupling was found to be a versatile tool for the cyclotrimerization of functionalized 1,10-phenathroline precursors. Due to the now improved processability, both liquid-crystalline behavior in the bulk phase and two-dimensional self-assembly at the molecular level could be studied, for the first time, for a torand system. The macrocycles exhibited a strong affinity for the complexation of different metal cations, as evidenced by MALDI-TOF analysis and spectroscopic methods. Experimental results were correlated to an extensive computational study of the cyclo-2,9-tris-1,10-phenanthroline cavity and its binding mode for metal cations. Due to the combination of several interesting features, toroidal macrocycles may find future applications in the field of ion and charge transport through molecular channels, as well as for chemical sensing and molecular writing in surface-confined monolayers under STM conditions.