灵活性很重要：共价有机框架和螺纹离子聚合物中的协同活性位点,Journal of the American Chemical Society

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灵活性很重要：共价有机框架和螺纹离子聚合物中的协同活性位点
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2016-11-28 , DOI: 10.1021/jacs.6b10629
Qi Sun ₁ , Briana Aguila ₁ , Jason Perman ₁ , Nicholas Nguyen ₁ , Shengqian Ma ₁

Affiliation

两个或多个反应中心在底物上协同工作以促进反应的组合现在被认为是催化领域的最新技术，但仍然存在巨大的挑战。这种类型的异构系统很少被利用，因为在刚性框架内空间分离的活性位点通常难以合作。现在事实证明，这个障碍是可以被超越的。这里介绍的策略的基本原理是将具有优异柔韧性和多孔多相催化剂的催化组分结合起来，正如将线性离子聚合物放置在靠近表面路易斯酸活性位点的位置，这些位点锚定在共价有机框架的壁上。 COF）。使用环氧化物和 CO2 的环加成反应作为模型反应，相对于单个催化组分，复合催化剂的活性得到了显着提高。此外，它们也明显优于由分子有机催化剂和多相路易斯酸催化剂组合形成的基准催化系统，同时提供额外的可回收性。线性聚合物上催化活性部分的非凡灵活性和富集浓度促进协同催化，从而导致优异的催化性能。因此，这项工作揭示了一种全新的设计具有双重活化行为的双功能催化剂的策略，并为设计模拟生物催化的多功能系统开辟了一条新途径。它们还明显优于由分子有机催化剂和多相路易斯酸催化剂组合形成的基准催化系统，同时提供额外的可回收性。线性聚合物上催化活性部分的非凡灵活性和富集浓度促进协同催化，从而导致优异的催化性能。因此，这项工作揭示了一种全新的设计具有双重活化行为的双功能催化剂的策略，并为设计模拟生物催化的多功能系统开辟了一条新途径。它们还明显优于由分子有机催化剂和多相路易斯酸催化剂组合形成的基准催化系统，同时提供额外的可回收性。线性聚合物上催化活性部分的非凡灵活性和富集浓度促进协同催化，从而导致优异的催化性能。因此，这项工作揭示了一种全新的设计具有双重活化行为的双功能催化剂的策略，并为设计模拟生物催化的多功能系统开辟了一条新途径。线性聚合物上催化活性部分的非凡灵活性和富集浓度促进协同催化，从而导致优异的催化性能。因此，这项工作揭示了一种全新的设计具有双重活化行为的双功能催化剂的策略，并为设计模拟生物催化的多功能系统开辟了一条新途径。线性聚合物上催化活性部分的非凡灵活性和富集浓度促进协同催化，从而导致优异的催化性能。因此，这项工作揭示了一种全新的设计具有双重活化行为的双功能催化剂的策略，并为设计模拟生物催化的多功能系统开辟了一条新途径。

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Flexibility Matters: Cooperative Active Sites in Covalent Organic Framework and Threaded Ionic Polymer

The combination of two or more reactive centers working in concert on a substrate to facilitate the reaction is now considered state of the art in catalysis, yet there still remains a tremendous challenge. Few heterogeneous systems of this sort have been exploited, as the active sites spatially separated within the rigid framework are usually difficult to cooperate. It is now shown that this roadblock can be surpassed. The underlying principle of the strategy presented here is the integration of catalytic components with excellent flexibility and porous heterogeneous catalysts, as demonstrated by the placement of linear ionic polymers in close proximity to surface Lewis acid active sites anchored on the walls of a covalent organic framework (COF). Using the cycloaddition of the epoxides and CO2 as a model reaction, dramatic activity improvements have been achieved for the composite catalysts in relation to the individual catalytic component. Furthermore, they also clearly outperform the benchmark catalytic systems formed by the combination of the molecular organocatalysts and heterogeneous Lewis acid catalysts, while affording additional recyclability. The extraordinary flexibility and enriched concentration of the catalytically active moieties on linear polymers facilitate the concerted catalysis, thus leading to superior catalytic performance. This work therefore uncovers an entirely new strategy for designing bifunctional catalysts with double-activation behavior and opens a new avenue in the design of multicapable systems that mimic biocatalysis.

更新日期：2016-11-28

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