Structures of (3n-crown-n)-Phenol (n= 4, 5, 6, 8) Host-Guest Complexes: Formation of a Uniquely Stable Complex for n= 6 via Collective Intermolecular Interaction
Structures of (3n-crown-n)-Phenol (n= 4, 5, 6, 8) Host-Guest Complexes: Formation of a Uniquely Stable Complex for n= 6 via Collective Intermolecular Interaction
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(3n-冠-n)-苯酚 (n= 4, 5, 6, 8) 主客体配合物的结构：通过集体分子间相互作用形成 n= 6 的独特稳定配合物
DOI：
10.1021/jz300313d
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发表时间：
2012
影响因子：
4.4
通讯作者：
and T. Ebata
中科院分区：
文献类型：
--
作者：
R. Kusaka;Y. Inokuchi;T. Haino;and T. Ebata
利用各种激光光谱方法研究了冠-酚1:1主客体配合物3n-冠-n[12C4(n= 4), 15C5(n= 5), 18C6(n= 6), 24C8(n= 8)]在气相中的结构。s1 - s1电子谱分别鉴定了12C4、15C5、18C6和24C8配合物的3、2、1和2个异构体，表明只有18C6 -苯酚形成一个独特的稳定配合物。在酚羟基和CH拉伸区进行红外光谱分析，发现这些配合物形成O···HO氢键，苯环参与了配合物的形成。分子力学理论分析和密度泛函理论计算也支持一个相当稳定的同分异构体的18c6 -苯酚。最稳定的18C6 -苯酚同分异构体在很大程度上是通过O··HO氢键、CH··π和O··HC（芳香）组成的集体分子间相互作用来稳定的，这样苯酚就像一把“锁和钥匙”一样被插入到18C6特定构象的空腔中。
Structures of crown–phenol 1:1 host–guest complexes, 3n-crown-n[12C4(n= 4), 15C5(n= 5), 18C6(n= 6), 24C8(n= 8)], in the gas phase have been studied by various laser spectroscopic methods. The S1–S0electronic spectra identified 3, 2, 1, and 2 isomers for the complexes of 12C4, 15C5, 18C6, and 24C8, respectively, suggesting that only 18C6–phenol forms one uniquely stable complex. The IR spectra in the phenolic OH and CH stretch regions indicate that these complexes form the O···HO hydrogen bond, and the benzene ring is involved in the complex formation. Theoretical analysis with molecular mechanics and density functional theory calculations also supports one considerably stable isomer for 18C6–phenol. The most stable 18C6–phenol isomer is largely stabilized through collective intermolecular interaction consisting of O···HO hydrogen bond, CH···π, and O···HC(aromatic) so that phenol is inserted into the cavity of a particular conformation of 18C6 like a “lock and key”.