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首页> 外文期刊>Chemistry: A European journal >Guest-responsive covalent frameworks by the cross-linking of liquid-crystalline salts: Tuning of lattice flexibility by the design of polymerizable units
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Guest-responsive covalent frameworks by the cross-linking of liquid-crystalline salts: Tuning of lattice flexibility by the design of polymerizable units

机译：通过液晶盐的交联反应来宾反应的共价框架：通过可聚合单元的设计调整晶格柔性

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摘要

Cross-linked polymers prepared by the in-situ polymerization of liquid-crystalline salts were found to work as solid-state hosts with a flexible framework. As a component of such hosts, four kinds of polymerizable amphiphilic carboxylic acids bearing alkyl chains with acryloyloxy (A), dienyl (D), and/or nonreactive (N) chain ends (monomeric carboxylic acids; M _(AAA), M _(ANA), M _(DDD), and M _(DND)) were used. The carboxylic acids were mixed with an equimolar amount of a template unit, (1R,2S)-norephedrine (guest amine; G _(RS)), to form the corresponding salts. Every salt exhibited a rectangular columnar LC phase at room temperature, which was successfully polymerized by ~(60)Co γ-ray-induced polymerization without serious structural disordering to afford the salt of cross-linked carboxylic acid (polymeric carboxylic acid; P _(AAA), P _(ANA), P _(DDD), and P _(DND)) with G _(RS). Owing to the noncovalency of the interactions between the polymer framework P and the template G _(RS), the cross-linked polymers could reversibly release and capture a meaningful amount of G _(RS). In response to the desorption and adsorption of G _(RS), the cross-linked polymers dramatically switched their nanoscale structural order. A systematic comparison of the polymers revealed that the choice of polymerizable groups has a significant influence on the properties of the resultant polymer frameworks as solid-state hosts. Among these polymers, P _(DDD) was found to be an excellent solid-state host, in terms of guest-releasing/capturing ability, guest-recognition ability, durability to repetitive usage, and unique structural switching mode.
机译：发现通过液晶盐的原位聚合制备的交联聚合物可作为具有柔性框架的固态主体。作为这类主体的组分，带有烷基链的四种可聚合的两亲羧酸具有丙烯酰氧基（A），二烯基（D）和/或非反应性（N）链端（单体羧酸; M_（AAA），M_ （ANA），M_（DDD）和M_（DND））。将羧酸与等摩尔量的模板单元（1R，2S）-去氧麻黄碱（来宾胺; G_（RS））混合，形成相应的盐。每种盐在室温下均呈矩形柱状LC相，可通过〜（60）Coγ射线诱导的聚合反应成功聚合，而不会发生严重的结构紊乱，从而得到交联羧酸的盐（聚合羧酸; P _（ AAA），P _（ANA），P _（DDD）和P _（DND））和G _（RS）。由于聚合物骨架P和模板G_（RS）之间相互作用的不共价，交联的聚合物可以可逆地释放并捕获有意义量的G_（RS）。响应于G_（RS）的解吸和吸附，交联的聚合物极大地改变了它们的纳米级结构顺序。聚合物的系统比较表明，可聚合基团的选择对所得聚合物骨架作为固态主体的性能有重大影响。在这些聚合物中，就客体释放/捕获能力，客体识别能力，对重复使用的耐久性以及独特的结构转换模式而言，P _（DDD）被认为是优异的固态主体。

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