Shape-selective crystallisation of fluxional carbon cages

被引:20
作者
Bismillah, Aisha N. [1 ]
Sturala, Jiri [1 ,2 ]
Chapin, Brette M. [1 ]
Yufit, Dmitry S. [1 ]
Hodgkinson, Paul [1 ]
McGonigal, Paul R. [1 ]
机构
[1] Univ Durham, Dept Chem, Stockton Rd, Durham DH1 3LE, England
[2] Univ Chem & Technol Prague, Dept Inorgan Chem, Tech 5, Prague 16628 6, Czech Republic
基金
英国工程与自然科学研究理事会;
关键词
X-RAY CRYSTALLOGRAPHY; COPE REARRANGEMENT; SOLID-STATE; REACTION PATHWAYS; C-13; NMR; CRYSTAL; CHEMISTRY; BULLVALENE; COMPLEXES; DEUTERIUM;
D O I
10.1039/c8sc04303e
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
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.
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页码:8631 / 8636
页数:7
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