A Halogen-Bonding Catenane for Anion Recognition and Sensing
A Halogen-Bonding Catenane for Anion Recognition and Sensing
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DOI：
10.1002/anie.201108404
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发表时间：
2012-01-01
影响因子：
16.6
通讯作者：
Beer, Paul D.
中科院分区：
文献类型：
--
作者：
Caballero, Antonio;Zapata, Fabiola;Beer, Paul D.
在过去的几十年里，阴离子超分子化学领域得到了极大的发展，这在很大程度上是由于负电荷物种在一系列化学、生物、医学和环境过程中所扮演的许多基本角色的实现。[1]通过将互补的静电、氢键、Lewis酸碱[2]和阴离子-π非共价相互作用[3]结合到无环和大环分子框架设计中，已经开发出许多高效的合成阴离子受体和传感器。然而，模拟生物阴离子结合蛋白表现出的选择性程度的挑战仍然存在。卤素键(XB)是缺乏电子、正极化的卤素原子(通常是溴或碘)与Lewis碱之间吸引人的非共价相互作用。[4]阴离子在导电、磁性和液晶材料的固态晶体工程[5]中被广泛用作XB受体。[6]鉴于XB S在严格的方向性和键强度方面与氢键互补类比，[7]令人惊讶的是，XB[8]在分子识别过程中的应用令人惊讶，如蛋白质-配体[9]络合物、阴离子受体化学、[10]和催化作用[11]现在才开始出现。通过使用阴离子模板，我们已经构建了三维互穿和互锁的分子宿主系统，这些系统主要通过静电和收敛的氢键对模板阴离子显示出高度的选择性。[12]为了显著影响互锁结合口袋的空间、电子和亲油特性，从而显著影响阴离子识别性能，我们最近报道了第一个XB-键合的轮紫杉烷，它含有一个碘三唑轴，它
The field of anion supramolecular chemistry has expanded enormously during the past few decades, inspired in large part by the realization of the many fundamental roles negatively charged species play in a range of chemical, biological, medical and environmental processes.[1] Through the incorporation of complementary electrostatic, hydrogen bonding, Lewis acid–base [2] and anion–π non-covalent interactions [3] into acyclic and macrocyclic molecular framework design, numerous efficient synthetic anion receptors and sensors have been developed. However, the challenge to mimic the degree of selectivity exhibited by biological anion-binding proteins still remains. Halogen bonding (XB) is the attractive noncovalent interaction between an electron-deficient, positively polarized halogen atom, commonly bromine or iodine, and a Lewis base.[4] Anions have been exploited extensively as XB acceptors in the solid state crystal engineering [5] of conducting, magnetic and liquid-crystalline materials.[6] Given XB s complementary analogy to hydrogen bonding in terms of stringent directionality and bond strength,[7] it is surprising that solution phase applications of XB [8] in molecular recognition processes such as protein–ligand [9] complexes, anion receptor chemistry,[10] and catalysis [11] are only now beginning to emerge.By using anion templation, we have constructed threedimensional interpenetrated and interlocked molecular host systems that exhibit a high degree of selectivity towards the templating anion through primarily electrostatics and convergent hydrogen bonding.[12] In an effort to influence significantly the steric, electronic and lipophilic characteristics, and hence anion recognition properties, of the interlocked binding pocket, we recently reported the first XB-bonding rotaxane containing an iodotriazolium axle which