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Cyclohexanone-Driven Discriminatory Behavior Change of Host Compound (+)-(2R,3R)-TETROL for Isomeric Methylcyclohexanone Guests
Crystal Growth & Design ( IF 3.2 ) Pub Date : 2017-11-16 00:00:00 , DOI: 10.1021/acs.cgd.7b01334 Benita Barton 1 , Sasha-Lee Dorfling 1 , Eric C. Hosten 1
Crystal Growth & Design ( IF 3.2 ) Pub Date : 2017-11-16 00:00:00 , DOI: 10.1021/acs.cgd.7b01334 Benita Barton 1 , Sasha-Lee Dorfling 1 , Eric C. Hosten 1
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Using appropriate competition experiments, host compound TETROL [(+)-(2R,3R)-1,1–4,4-tetraphenylbutane-1,2,3,4-tetraol] was revealed to discriminate between the isomeric methylcyclohexanone guests; the host selectivity was in the order 2- ≫ 3- > 4- methylcyclohexanone. Surprisingly, addition of unsubstituted cyclohexanone to these competitions instigated a complete reversal in the host’s preference for the alkylcyclohexanones: a selectivity order of cyclohexanone >4- > 3- > 2-methylcyclohexanone was attained. It is proposed that it is the significant preference of TETROL for cyclohexanone that is responsible for the host behavior change in the presence of this guest. As evidence, the crystal packing of a mixed complex, TETROL·(72%)cyclohexanone·(28%)4-methylcyclohexanone, was shown to be isostructural with pure TETROL·cyclohexanone (which differs from TETROL·4-methylcyclohexanone). The addition of cyclohexanone to the competition experiments therefore steers crystallization toward crystals with similar packing to that of the preferred guest complex accounting for TETROL’s change in selectivity in the presence of this guest. Hirshfeld surface analyses were used to demonstrate that TETROL·cyclohexanone experiences a significantly larger number of stabilizing O···H/H···O interactions (15.2%) compared with the other complexes (11.5–14.4%), accounting for the host’s overwhelming preference for this guest. Thermogravimetric analysis further confirmed that cyclohexanone was more strongly bound in the crystal than the other guests.
中文翻译：
异构甲基环己酮对主体化合物（+）-（2 R，3 R）-TETROL的环己酮驱动的歧视行为变化
使用适当的竞争实验，宿主化合物TETROL [（+）-（2 R，3 R）-1,1–4,4-四苯基丁烷-1,2,3,4-四醇]可以区分异构的甲基环己酮客体；主体选择性为2- 2-3-＞ 4-甲基环己酮。出人意料的是，在这些竞争中加入未取代的环己酮使宿主对烷基环己酮的偏好发生了完全逆转：环己酮的选择性顺序> 4-> 3-> 2-甲基环己酮。有人提出，TETROL对环己酮的显着偏爱是导致该来宾在宿主行为发生变化的原因。作为证据，混合纯TETROL·（72％）环己酮·（28％）4-甲基环己酮的晶体堆积被证明与纯TETROL·环己酮是同构的（不同于TETROL·4-甲基环己酮）。因此，在竞争实验中加入环己酮会使结晶趋向具有与优选客体配合物相似堆积的晶体，这解释了TETROL在该客体存在下的选择性变化。Hirshfeld表面分析表明，TETROL·环己酮经历的稳定化O···H / H···O相互作用数量（15.2％）比其他配合物（11.5-14.4％）要大得多，占宿主的对此客人压倒性的偏好。热重分析进一步证实，环己酮在晶体中的结合力比其他客体更高。
更新日期：2017-11-16
中文翻译：
异构甲基环己酮对主体化合物（+）-（2 R，3 R）-TETROL的环己酮驱动的歧视行为变化
使用适当的竞争实验，宿主化合物TETROL [（+）-（2 R，3 R）-1,1–4,4-四苯基丁烷-1,2,3,4-四醇]可以区分异构的甲基环己酮客体；主体选择性为2- 2-3-＞ 4-甲基环己酮。出人意料的是，在这些竞争中加入未取代的环己酮使宿主对烷基环己酮的偏好发生了完全逆转：环己酮的选择性顺序> 4-> 3-> 2-甲基环己酮。有人提出，TETROL对环己酮的显着偏爱是导致该来宾在宿主行为发生变化的原因。作为证据，混合纯TETROL·（72％）环己酮·（28％）4-甲基环己酮的晶体堆积被证明与纯TETROL·环己酮是同构的（不同于TETROL·4-甲基环己酮）。因此，在竞争实验中加入环己酮会使结晶趋向具有与优选客体配合物相似堆积的晶体，这解释了TETROL在该客体存在下的选择性变化。Hirshfeld表面分析表明，TETROL·环己酮经历的稳定化O···H / H···O相互作用数量（15.2％）比其他配合物（11.5-14.4％）要大得多，占宿主的对此客人压倒性的偏好。热重分析进一步证实，环己酮在晶体中的结合力比其他客体更高。
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