A Springloaded Metal-Ligand Mesocate Allows Access to Trapped Intermediates of Self-Assembly
A Springloaded Metal-Ligand Mesocate Allows Access to Trapped Intermediates of Self-Assembly
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DOI：
10.1021/acs.inorgchem.8b00370
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发表时间：
2018-04-02
影响因子：
4.6
通讯作者：
Hooley, Richard J.
中科院分区：
文献类型：
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作者：
Bogie, Paul M.;Holloway, Lauren R.;Hooley, Richard J.
应变的Fe2L3亚氨基吡啶中间体在与竞争性二胺的组装后反应中表现出高度可变的反应性。在常温下，应变的组装可以在几分钟内对过渡起反应，并允许观察到自组装途径中的动力学捕获的中间产物。当使用在完全平衡时只能形成不太受欢迎的笼状产物的二胺时，选择性地形成带有侧链的捕获的ML3碎片，而是选择性地形成“悬挂”的NH2基团。二胺结构的微小变化对产物的结果有很大的影响：在温和的条件下，较少的刚性二胺将中间相转化为更受欢迎的自组装笼状络合物，并允许在置换路径中观察到杂络中间体。中位化合物允许通过添加的亚组分结构的微小迭代变化来控制平衡过程和产品结果的方向，并提供了一种在多组分Fe-亚胺基吡啶自组装中通常观察不到的金属-配体笼状结构的方法。
A strained, "springloaded" Fe2L3 iminopyridine mesocate shows highly variable reactivity upon postassembly reaction with competitive diamines. The strained assembly is reactive toward transimination in minutes at ambient temperature and allows observation of kinetically trapped intermediates in the self-assembly pathway. When diamines are used that can only form less favored cage products upon full equilibration, trapped ML3 fragments with pendant, "hanging" NH2 groups are selectively formed instead. Slight variations in diamine structure have large effects on the product outcome: less rigid diamines convert the mesocate to more favored self-assembled cage complexes under mild conditions and allow observation of heterocomplex intermediates in the displacement pathway. The mesocate allows control of equilibrium processes and direction of product outcomes via small, iterative changes in added subcomponent structure and provides a method of accessing metal-ligand cage structures not normally observed in multicomponent Fe-iminopyridine self-assembly.