Ma Suxiang, Chen Huanqing, Li Jian, Jia Xueshun, Li Chunju
School of Chemical and Environmental Engineering, Shanghai Institute of Technology, Shanghai, 201418, P.R. China.
Department of Chemistry, Center for Supramolecular Chemistry and Catalysis, Shanghai University, Shanghai, 200444, P.R. China.
Chem Asian J. 2016 Dec 6;11(23):3449-3453. doi: 10.1002/asia.201601373. Epub 2016 Nov 22.
Biphen[n]arenes (n=3, 4) are a new family of macrocyclic hosts. Here, we describe the molecular recognition behavior of hydroxylated biphen[4]arene (OHBP4) for the first time. A series of cationic guests with different sizes and shapes, including quaternary ammonium salts (1⋅PF and 2⋅PF ), pyridinium-based guests (3⋅2 PF -6⋅2 PF ), and cobaltocenium hexafluorophosphate (7⋅PF ), were chosen as model guest molecules. OHBP4 exhibits good selectivity towards the 2,7-dibutyldiazapyrenium bis(hexafluorophosphate) (4⋅2 PF ) axle to form a [2]pseudorotaxane-type complex. In contrast, hydroxylated biphen[3]arene (OHBP3) cannot bind with this big guest. In addition, OHBP4 strongly interacts with adamantane derivative 2⋅PF and cobaltocenium 7⋅PF , which have tridimensional shape and relatively large size. The association constant of the 7 ⊂OHBP4 complex in 1:1 (v/v) [D ]acetone/CD Cl solution is up to 3100±300 m .
联苯[n]芳烃（n = 3, 4）是一类新型大环主体化合物。在此，我们首次描述了羟基化联苯[4]芳烃（OHBP4）的分子识别行为。选择了一系列具有不同尺寸和形状的阳离子客体，包括季铵盐（1·PF和2·PF）、吡啶鎓基客体（3·2 PF - 6·2 PF）以及六氟磷酸钴茂（7·PF）作为模型客体分子。OHBP4对2,7 - 二丁基二氮杂芘双（六氟磷酸盐）（4·2 PF）轴表现出良好的选择性，形成[2]准轮烷型配合物。相比之下，羟基化联苯[3]芳烃（OHBP3）不能与这种大客体结合。此外，OHBP4与具有三维形状和相对较大尺寸的金刚烷衍生物2·PF和钴茂7·PF强烈相互作用。在1:1（v/v）[D]丙酮/CDCl溶液中，7⊂OHBP4配合物的缔合常数高达3100±300 m。
