Homochiral [2.2]Paracyclophane Self-Assembly Promoted by Transannular Hydrogen Bonding
Homochiral [2.2]Paracyclophane Self-Assembly Promoted by Transannular Hydrogen Bonding
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DOI：
10.1002/anie.201605286
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发表时间：
2016-08-26
影响因子：
16.6
通讯作者：
Castellano, Ronald K.
中科院分区：
文献类型：
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作者：
Fagnani, Danielle E.;Meese, Michael J., Jr.;Castellano, Ronald K.
[2.2]对环芳烷（pCp）与许多结构单元不同，在超分子结构中实际上尚未被探索。这里报道的是第一个能够在溶液和固态中编程自组装成扩展共面堆叠的 pCp 衍生物的合成和表征。该设计在 pCp-4,7,12,15-四甲酰胺 (pCpTA) 的伪邻位酰胺之间采用迄今为止在 pCps 中尚未研究的跨环（分子内）氢键（H 键）来预组织分子，以与堆叠的邻居形成分子间氢键。 X 射线晶体学证实了同手性、一维 pCpTA 堆叠的形成，该堆叠由两条氢键链螺旋状连接。手性意义由 pCpTA 单体的平面手性（R-p 或 S-p）决定。核磁共振、红外和紫外/可见光研究的结合证实了第一个超分子 pCp 聚合物在溶液中的形成。
[2.2]paracyclophane (pCp), unlike many -building blocks, has been virtually unexplored in supramolecular constructs. Reported here is the synthesis and characterization of the first pCp derivatives capable of programmed self-assembly into extended cofacial -stacks in solution and the solid state. The design employs transannular (intramolecular) hydrogen bonds (H-bonds), hitherto unstudied in pCps, between pseudo-ortho-positioned amides of a pCp-4,7,12,15-tetracarboxamide (pCpTA) to preorganize the molecules for intermolecular H-bonding with -stacked neighbors. X-ray crystallography confirms the formation of homochiral, one-dimensional pCpTA stacks helically laced with two H-bond strands. The chiral sense is dictated by the planar chirality (R-p or S-p) of the pCpTA monomers. A combination of NMR, IR, and UV/Vis studies confirms the formation of the first supramolecular pCp polymers in solution.