Supramolecular polymers with tunable topologies via hierarchical coordination-driven self-assembly and hydrogen bonding interfaces
Supramolecular polymers with tunable topologies via hierarchical coordination-driven self-assembly and hydrogen bonding interfaces
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DOI：
10.1073/pnas.1307472110
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发表时间：
2013-09
期刊：
影响因子：
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通讯作者：
Xuzhou Yan;Shijun Li;J. B. Pollock;Timothy R. Cook;Jianzhuang Chen;Yanyan Zhang;Xiaofan Ji;Y. Yu-Y.-Y
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文献类型：
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作者：
Xuzhou Yan;Shijun Li;J. B. Pollock;Timothy R. Cook;Jianzhuang Chen;Yanyan Zhang;Xiaofan Ji;Y. Yu-Y.-Y
自下而上通过分级自组装构建非共价键合的超分子材料是获得复杂超分子材料的有力策略。该组装过程涉及逐步、均匀地增加基底的结构复杂性，从离散的前体开始，通过受控的反应性在维度上增长到最终产品。在此，利用两个正交过程：协调驱动的自组装和氢键。前者依赖于金属-配体键的可预测的形成，其中所使用的刚性前体的方向性决定了结构结果。后者使用2-脲基-4-嘧啶酮界面，其由于可在亚基之间发生的四重氢键而在结构上是稳健的。通过将这两个过程结合到一个单一的系统中，有可能产生保持与离散的超分子配位络合物相关的有吸引力的可调谐性的分级材料。例如，通过简单地选择不同的金属受体前体作为组装组分，包含连接的金属-长菱形的一维链的合成容易地适应于2D交联的六边形网络。亚基之间的特定相互作用，在这种情况下，铂（II）-吡啶基键和四重H-键的脲基嘧啶酮，是不变的，建立一个独特的策略，以获得超分子聚合物与显着的拓扑结构差异与最小的合成重新设计。此外，由包含铂金属杂环所施加的结构刚性用于使环状低聚物的形成最小化，增加形成的功效并改善所得材料的性质。此外，这项研究还挖掘了有机铂（II）金属环在材料科学中的潜力。
A powerful strategy to obtain complex supramolecular materials is the bottom-up construction of noncovalently bound materials by hierarchical self-assembly. This assembly process involves stepwise, uniform increases to the architectural complexity of a substrate, starting from discrete precursors and growing in dimensionality through controlled reactivity to a final product. Herein, two orthogonal processes are exploited: coordination-driven self-assembly and hydrogen bonding. The former relies on the predictable formation of metal–ligand bonds wherein the directionalities of the rigid precursors used determines the structural outcome. The latter uses 2-ureido-4-pyrimidinone interfaces that are structurally robust by virtue of the quadruple hydrogen bonding that can occur between subunits. By combining these two processes into a single system, it is possible to generate hierarchical materials that preserve the attractive tunability associated with discrete supramolecular coordination complexes. For instance, the synthesis of a one-dimensional chain comprising linked metalla-rhomboids is readily adapted to a 2D cross-linked hexagonal network by simply selecting a different metal acceptor precursor as an assembly component. The specific interactions between subunits, in this case platinum(II)-pyridyl bonds and the quadruple H-bonding of ureidopyrimidinone, are unchanged, establishing a unique strategy to obtain supramolecular polymers with marked topological differences with minimal synthetic redesign. In addition, the structural rigidity imposed by the inclusion of the platinum metallacycles serves to minimize the formation of cyclic oligomers, increasing the efficacy of formation and improving the properties of the resultant materials. Furthermore, this study taps the potential of organoplatinum(II) metallacycles in materials science.