Molecular Recognition of Hydrocarbon Guests by a Supramolecular Capsule Formed by the 4:4 Self-Assembly of Tris(Zn2+-Cyclen) and Trithiocyanurate in Aqueous Solution
Molecular Recognition of Hydrocarbon Guests by a Supramolecular Capsule Formed by the 4:4 Self-Assembly of Tris(Zn2+-Cyclen) and Trithiocyanurate in Aqueous Solution
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DOI：
10.1002/asia.201100871
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发表时间：
2012-05-01
影响因子：
4.1
通讯作者：
Kimura, Eiichi
中科院分区：
文献类型：
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作者：
Aoki, Shin;Suzuki, Satoshi;Kimura, Eiichi
我们之前报道过三聚体Zn2+环环配合物（tris(Zn2+cyclen), [Zn3L1]6+）和三硫氰酸三阴离子（TCA3-）在中性水溶液中以4:4的比例组装形成一个立方面体超分子笼[(Zn3L1)4(TCA3-)4]12+（以下简称锌笼）（cyclen=1,4,7,10-四氮杂环十二烷）。本文研究了常压下锌笼对C1C12烃类(CnH（2n+2) (n112)）、环戊烷、环十二烷、顺式十烷和反式十烷的分子识别。这种笼状复合物还能够封装比锌笼内腔体积更大的客体分子，从而表明锌笼的内部形状是灵活的。Zncageguest配合物的计算模拟支持了这一结论。此外，计算了锌笼主体、客体分子和锌笼-客体配合物的溶剂可及表面积（SASA），并用该数据解释了客体替代实验确定的稳定性顺序。讨论了锌笼对水溶液中挥发性分子的储存。
We have previously reported that the trimeric Zn2+cyclen complex (tris(Zn2+cyclen), [Zn3L1]6+) and the trianion of trithiocyanuric acid (TCA3-) assembled in a 4:4 ratio to form a cuboctahedral supramolecular cage, [(Zn3L1)4(TCA3-)4]12+ (hereafter referred to as a Zncage), in neutral aqueous solution (cyclen=1,4,7,10-tetraazacyclododecane). Herein, we examined the molecular recognition of C1C12 hydrocarbons (CnH(2n+2) (n112)), cyclopentane, cyclododecane, cis-decalin, and trans-decalin by the Zncage under normal atmospheric pressure. This cage complex was also able to encapsulate guest molecules that had larger volumes than that of the inner cavity of the Zncage, thereby suggesting that the inner shape of the Zncage was flexible. Computational simulations of Zncageguest complexes provided support for this conclusion. Moreover, the solvent-accessible surface areas (SASA) of the Zncage host, guest molecules, and the Zncage-guest complexes were calculated and the data were used to explain the order of stability determined by the guest-replacement experiments. The storage of volatile molecules in aqueous solution by the Zncage is also discussed.