Herein we demonstrate that the rapid ‘shapeshifting’ constitutional isomerization of a substituted bullvalene is influenced by the E to Z configurational isomerization of a remote carbamate group, giving rise to correlated motion. We find that, while the E configurational isomer of a bulky carbamate favors the β-bullvalene constitutional isomer, a noncovalent bonding interaction within the Z carbamate tips the equilibrium toward the γ-bullvalene form. Using DFT modelling and NMR spectroscopy, this long-range interaction is identified as being between the bullvalene core and a pendant phenyl group connected to the carbamate. Coupling the constitutional changes of a bullvalene to a reciprocal configurational isomerization through a long-range interaction in this way will allow shapeshifting rearrangements to be exploited as part of collective motion in extended structures.

中文翻译：

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相关的变形和构型异构化


在此，我们证明了取代的牛瓦烯的快速“变形”结构异构化受到远程氨基甲酸酯基团的E至Z构型异构化的影响，从而引起相关运动。我们发现，虽然大体积氨基甲酸酯的 E 构型异构体有利于 β-布瓦烯构型异构体，但 Z 氨基甲酸酯内的非共价键相互作用使平衡偏向 γ-布瓦烯形式。使用 DFT 建模和核磁共振波谱，这种长程相互作用被确定为 bullvalene 核心和连接到氨基甲酸酯的侧苯基之间的相互作用。以这种方式通过长程相互作用将牛瓦烯的结构变化与相互构型异构化耦合，将允许利用变形重排作为扩展结构中集体运动的一部分。