Supramolecular assemblies of chiral propargylic alcohols.
Supramolecular assemblies of chiral propargylic alcohols.
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手性炔丙醇的超分子组装体。
DOI：
10.1002/anie.200601594
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发表时间：
2006
期刊：
影响因子：
--
通讯作者：
Pu,Lin
中科院分区：
文献类型：
--
作者：
Hyacinth,Marilise;Chruszcz,Maksymilian;Lee,KiSung;Sabat,Michal;Gao,Ge;Pu,Lin
由交替的R和S对映体形成（图1）。六聚体通过O··· O氢键结合在一起，O··· O供体-受体距离为2.808、2.771和2.777。五氟苯基环和苯基环几乎完全平行，环平面之间的平均间距为3.52。额外的稳定性来自苯环的邻位C2 H基团和五氟苯基环的邻位C2F基团之间的C2 H···F·C氢键网络，C··· F间距为3.25、3.36和3.27，与有机氟原子系统中发现的类似距离相当。[6]rac-1的六聚体结构通过苯乙炔基-五氟苯基π-π相互作用沿晶胞轴沿着堆叠形成无限大的孔道。在rac-1的六聚体单元中，三个R对映体向上，三个S对映体向下（图2a）。通道中的两个堆叠六聚体产生可以包括客体分子（诸如二氧杂环己烷和二氯甲烷）的笼。图2b是rac-1晶体结构中一个通道的横截面，显示了两个笼，每个笼包含一个二氧杂环己烷分子。图2c给出了rac-I中两个笼的尺寸。每个融合器的直径A和B分别为7.85和8.35。
formed by alternating R and S enantiomers (Figure 1). The hexamers are held together by OÀH··· O hydrogen bonds with O··· O donor–acceptor distances of 2.808, 2.771, and 2.777. The pentafluorophenyl and phenyl rings are almost exactly parallel, with an average separation of 3.52 between the ring planes. Additional stabilization comes from a network of CÀH··· FÀC hydrogen bonds between the ortho CÀH groups of the phenyl ring and the ortho CÀF groups of the pentafluorophenyl ring, with the C··· F separations of 3.25, 3.36, and 3.27 comparable with analogous distances found in systems with organic fluorine atoms.[6] The hexameric structures of rac-1 stack with each other along the unit-cell axis with the alternating parallel phenylethynyl–pentafluorophenyl π–π interaction to form infinite channels. In a hexameric unit of rac-1, three R enantiomers are up and three S enantiomers are down (Figure 2a). The two stacking hexamers in a channel generate a cage that can include guest molecules, such as dioxane and dichloromethane. Figure 2b is the cross section of one channel in the crystal structure of rac-1 and shows two cages, with each including a dioxane molecule. Figure 2c gives the dimension of two cages in rac-1. The diameters A and B are 7.85 and 8.35 for each cage, respectively.