Solid-state hosts by the template polymerization of columnar liquid crystals: Locked supramolecular architectures around chiral 2-amino alcohols
Solid-state hosts by the template polymerization of columnar liquid crystals: Locked supramolecular architectures around chiral 2-amino alcohols
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DOI：
10.1002/chem.200601656
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发表时间：
2007-01-01
影响因子：
4.3
通讯作者：
Saigo, Kazuhiko
中科院分区：
文献类型：
--
作者：
Amano, Sayaka;Ishida, Yasuhiro;Saigo, Kazuhiko
多组分液晶的交联可以应用于具有明确结构的纳米多孔材料的合成。在这项工作中，我们展示了由羧酸和对映体纯2-氨基醇的盐组成的柱状液晶的模板聚合，以及其中之一作为固态宿主的应用。3，4，5-三（11-丙烯酰氧基十一烷氧基）苯甲酸与（S）2-氨基-1-丙醇和（1 R，2S）去甲麻黄碱的盐分别具有六方和矩形柱状液晶结构。γ射线诱导聚合成功地应用于液晶盐的交联，从克级制备具有均匀柱状结构的聚合物时保留原始结构顺序的角度来看，这比光诱导聚合更有利。由此从没食子酸衍生物和（1 R，2S）-去甲麻黄碱获得的交联聚合物可用作通过酸-胺相互作用从客体溶液中捕获胺的非均相主体。当（1 R，2S）-去甲麻黄碱被替换为其他胺通过客人交换反应，观察到的“模板效应”，客人的大小和形状的客人交换效率的决定因素。当外消旋2-氨基醇被用作客体时，客体吸附被发现以对映选择性的方式进行，特别是在C1-位具有庞大取代基的底物的情况下。客体的偏好再次阐明的模板效应，虽然对映选择模式切换取决于C2取代基的存在。
The cross-linking of multicomponent liquid crystals could be applied to the synthesis of nanometersized porous materials with a well-defined structure. In this work we demonstrate the template polymerization of columnar liquid crystals composed of the salts of a carboxylic acid and enantiopure 2-amino alcohols, and the application of one of them as a solid-state host. The salts of 3,4,5-tris(11-acryloyloxyundecyloxy)benzoic acid with (S)2-amino-1-propanol and with (1R,2S)norephedrine showed hexagonal and rectangular columnar liquid-crystalline structures, respectively. ne successful application of gamma-ray-induced polymerization to the cross-linking of the liquid-crystalline salts, which was more advantageous than photoinduced polymerization from the standpoint of the retention of the original structural order in the gram-scale preparation of the polymers with a homogeneous columnar structure. The cross-linked polymer thus obtained from the gallic acid derivative and (1R,2S)-norephedrine was applicable as a heterogeneous host to capture amines from a guest solution through acid-amine interactions. When (1R,2S)-norephedrine was replaced with other amines through the guest-exchange reaction, a "template effect" was observed; the size and shape of the guests were determining factors for the efficiency of the guest exchange. The guest adsorption was found to proceed in an enantioselective manner when racemic 2-amino alcohols were used as guests, especially in the cases of substrates possessing a bulky substituent at the C1-position. The guest preference was again elucidated by the template effect, although the enantioselection mode was switched depending on the presence of a C2 substituent.