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首页> 外文期刊>Chemistry: A European journal >High-Barrier Molecular Balance for Studying Face-to-Face Arene–Arene Interactions in the Solid State and in Solution
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High-Barrier Molecular Balance for Studying Face-to-Face Arene–Arene Interactions in the Solid State and in Solution

机译：用于研究固态和溶液中面对面的Arene-Arene相互作用的高阻隔分子平衡

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摘要

An atropisomeric molecular balance was developed to study faceto- face arene–arene interactions. The balance has a large central 1,4,5,8- naphthalene diimide surface that forms intramolecular arene–arene interactions with two pendent arms. The balance adopts distinct syn and anti isomers with varying numbers of intramolecular interactions. Thus, the strength of the arene–arene interaction could be quantitatively measured by NMR spectroscopy from the anti/syn ratios. The size of the arene arms was easily varied, which allowed examination of the relationship between arene size and strength of the interaction. A nonlinear size dependence was observed in solution with larger arene arms having a disproportionately stronger arene– arene interaction. The intramolecular arene–arene interactions were also characterized in the solid state by Xray crystallography. These studies were facilitated by the kinetic stability of the syn and anti isomers at room temperature due to the high isomerization barrier (DG=27.0 kcalmol~(-1)). Thus, the anti isomer could be selectively isolated and crystallized in its folded conformation.The X-ray structures confirmed that the anti isomers formed two strong intramolecular arene–arene interactions with face-to-face geometries. The solid-state structure analysis also reveals that the rigid framework may contribute to the observed nonlinear size trend. The acetate linker is slightly too long, which selectively destabilizes the balances with smaller arene arms.The larger arene arms are able to compensate for the longer linker and form effective intramolecular arene–arene interactions.
机译：开发了一种阻转异构分子平衡来研究面对面的芳烃与芳烃之间的相互作用。天平具有较大的中心1,4,5,8-萘二酰亚胺表面，该表面与两个侧臂形成分子内的芳烃-芳烃相互作用。天平采用不同数量的分子间相互作用的顺式和反式异构体。因此，芳烃-芳烃相互作用的强度可以通过NMR光谱从反/同比率进行定量测量。芳烃臂的大小很容易变化，这可以检查芳烃大小与相互作用强度之间的关系。在较大的芳烃臂中，芳烃与芳烃的相互作用不成比例地存在非线性大小依赖性。分子内的芳烃-芳烃相互作用还通过X射线晶体学表征为固态。由于高的异构化势垒（DG = 27.0 kcalmol〜（-1）），顺式和反式异构体在室温下的动力学稳定性促进了这些研究。因此，可以选择性地分离出反异构体并使其折叠构型结晶。X射线结构证实，这些反异构体形成了两个强烈的分子内芳烃-芳烃相互作用，并具有面对面的几何形状。固态结构分析还表明，刚性框架可能有助于观察到的非线性尺寸趋势。乙酸酯连接基太长，会选择性地破坏较小的芳烃臂的平衡。较大的芳烃臂能够补偿较长的连接基并形成有效的分子内芳烃与芳烃的相互作用。

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