Activation of Positive Cooperativity by Size‐Mismatch Assembly via Inclination of Guests in a Single‐Site Receptor
Activation of Positive Cooperativity by Size‐Mismatch Assembly via Inclination of Guests in a Single‐Site Receptor
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通过单位点受体中客体的倾向通过尺寸不匹配组装激活正协同性
DOI：
10.1002/asia.202200076
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发表时间：
2022
期刊：
影响因子：
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通讯作者：
Isobe Hiroyuki
中科院分区：
文献类型：
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作者：
Matsuno Taisuke;Takahashi Kanato;Ikemoto Koki;Isobe Hiroyuki
卤化碗状客体碳烯被包裹在圆柱形主体[4]环丙烯腈中，形成碗状管状复合物，模拟碗状客体与碳纳米管之间的超分子复合物。与碳纳米管一样，[4]环乙烯的圆柱形空间将多个环烯分子捕获成阵列，并且通常与含有各种卤素取代基（F, Cl， Br和I）的环烯客体形成1:1的配合物。对等温滴定量热数据的仔细统计分析成功地揭示了化学计量，并通过X射线晶体学分析进一步阐明了1:1配合物的分子结构。两个氟化聚能客体垂直于圆柱体轴线堆叠，而两个氯化聚能客体以倾斜方向堆叠。结构上的差异导致了溶液中两阶段结合的协同性差异很大：氟化环烯客体在1:1配位反应中表现出负协同性，而其他较大的卤化环烯客体则表现出正协同性。
A halogenated bowl‐shaped guest, corannulene, was encapsulated in a cylindrical host, [4]cyclochrysenylene, to form a bowl‐in‐tube complex, which mimicked supramolecular complexes between bowl guests and carbon nanotubes. As was the case with carbon nanotubes, the cylindrical space of [4]cyclochrysenylene trapped multiple corannulene molecules in an array, and 1 : 2 complexes were commonly obtained with the corannulene guests with various halogen substituents (F, Cl, Br and I). Careful statistical analyses of isothermal titration calorimetry data succeeded in revealing the stoichiometry, and the molecular structures of the 1 : 2 complexes were further clarified by X‐ray crystallographic analyses. Two fluorinated corannulene guests were stacked perpendicular to the cylinder axis, while two chlorinated guests were stacked with inclined orientations. The structural difference resulted in a large difference in the cooperativity of the two‐stage association in solution: fluorinated corannulene guests showed negative cooperativity for the 1 : 2 complexation, and the other, larger halogenated corannulene guests showed positive cooperativity.