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Shape-selective crystallisation of fluxional carbon cages†
Chemical Science ( IF 7.6 ) Pub Date : 2018-10-22 00:00:00 , DOI: 10.1039/c8sc04303e
Aisha N Bismillah 1 , Jiri Sturala 1 , Brette M Chapin 1 , Dmitry S Yufit 1 , Paul Hodgkinson 1 , Paul R McGonigal 1
Affiliation  

Dynamic covalent rearrangements of fluxional carbon cages, such as bullvalenes and barbaralanes, impart ‘shapeshifting’ molecular properties. Here, a series of five barbaralanes each interconvert dynamically between two constitutional isomers in solution, but resolve to single isomers upon crystallisation. Unexpectedly, the minor solution-phase isomers are resolved in two instances. Through dynamic NMR, crystallographic and DFT analyses, we show that the isomer observed in the solid state is not a direct consequence of the equilibrium distribution in solution or any specific noncovalent interactions. Rather, the dynamic preferential crystallisation is dictated by differences in molecular size and shape.

中文翻译:


流动碳笼的择形结晶†



流变碳笼(例如 Bullvalenes 和 Barbaralanes)的动态共价重排赋予“变形”分子特性。在此,一系列五种巴巴拉烷在溶液中的两种结构异构体之间动态地相互转化,但在结晶时分解为单一异构体。出乎意料的是,少量溶液相异构体在两种情况下得到了解析。通过动态核磁共振、晶体学和密度泛函分析,我们表明在固态中观察到的异构体并不是溶液中平衡分布或任何特定非共价相互作用的直接结果。相反,动态优先结晶是由分子大小和形状的差异决定的。
更新日期:2018-10-22
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