Ziganshin Marat A, Yakimov Alexey V, Safina Goulnaz D, Solovieva Svetlana E, Antipin Igor S, Gorbatchuk Valery V
Institute of Chemistry, Kazan State University, Kremlevskaya 18, Kazan, 420008, Russia.
Org Biomol Chem. 2007 May 7;5(9):1472-8. doi: 10.1039/b701082f. Epub 2007 Apr 4.
The effect of macrocycle size on the structure-property relationships was studied for inclusion compounds of tert-butylcalix[n]arenes (n=4,5) with volatile organic guests having various molecular size and group composition. Vapor-sorption isotherms, guest-inclusion stoichiometry and Gibbs energy, thermostability parameters and decomposition enthalpies were determined for host-guest compounds (clathrates) obtained using saturation of solid calixarene powder with guest vapor. The increase of the host macrocycle in the studied calixarene pair changes the observed structure-property relationship from the guest-binding selectivity mostly seen in inclusion Gibbs energy to the high sensitivity for guest structure in inclusion stoichiometry. The host with the larger macrocycle has more clathrates with stepwise formation and decomposition. Specific types of guest binding with solid hosts are discussed.
研究了大环尺寸对叔丁基杯[n]芳烃（n = 4,5）与具有不同分子大小和基团组成的挥发性有机客体形成的包合物结构-性质关系的影响。通过用客体蒸气使固体杯芳烃粉末饱和得到主客体化合物（笼合物），测定了其蒸气吸附等温线、客体包合化学计量比和吉布斯自由能、热稳定性参数以及分解焓。在所研究的杯芳烃对中，主体大环尺寸的增加改变了观察到的结构-性质关系，从主要在包合吉布斯自由能中看到的客体结合选择性，转变为在包合化学计量比中对客体结构的高敏感性。具有较大大环的主体有更多具有逐步形成和分解过程的笼合物。讨论了客体与固体主体结合的特定类型。
