Lankshear Michael D, Evans Nicholas H, Bayly Simon R, Beer Paul D
Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford, OX1 3QR, UK.
Chemistry. 2007;13(14):3861-70. doi: 10.1002/chem.200700041.
We present the rational design and anion-binding properties of the first anion-templated pseudorotaxanes and catenanes in which the "wheel" component is provided by a calix[4]arene macrobicyclic unit. The designs and syntheses of two new calix[4]arene macrobicycles, 2 and 3, are presented, and the abilities of these new species both to bind anions and to undergo anion-dependent pseudorotaxane formation are demonstrated. Furthermore, it is shown that performing ring-closing metathesis reactions on some of these pseudorotaxane assemblies gives novel catenane species 14 and 15, in which the yield of interlocked molecule obtained is critically dependent on the presence of a suitable anion template, namely, chloride. Exchange of the chloride anion in catenane 14 a for hexafluorophosphate gives catenane 14 d, which contains a unique anion-binding domain defined by the permanently interlocked hydrogen-bond-donating calix[4]arene macrobicycle and pyridinium macrocycle fragments. The anion-binding properties of this domain are presented, and shown to differ from non-interlocked components.
我们展示了首例阴离子模板化准轮烷和索烃的合理设计及其阴离子结合特性，其中“轮”组件由杯[4]芳烃大环单元提供。介绍了两种新型杯[4]芳烃大环化合物2和3的设计与合成，并证明了这些新化合物结合阴离子以及进行阴离子依赖的准轮烷形成的能力。此外，研究表明，对其中一些准轮烷组装体进行关环复分解反应可得到新型索烃化合物14和15，其中互锁分子的产率严重依赖于合适的阴离子模板（即氯离子）的存在。将索烃14 a中的氯离子交换为六氟磷酸根得到索烃14 d，其包含一个独特的阴离子结合域，该结合域由永久互锁的氢键供体杯[4]芳烃大环和吡啶鎓大环片段定义。展示了该结合域的阴离子结合特性，并表明其与非互锁组件不同。
