Photoswitchable Sol-Gel Transitions and Catalysis Mediated by Polymer Networks with Coumarin-Decorated Cu24 L24 Metal-Organic Cages as Junctions.,Angewandte Chemie International Edition

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Photoswitchable Sol-Gel Transitions and Catalysis Mediated by Polymer Networks with Coumarin-Decorated Cu24 L24 Metal-Organic Cages as Junctions.
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2020-01-16 , DOI: 10.1002/anie.201913297
Nathan J Oldenhuis ₁ , K Peter Qin ₁ , Shu Wang ₂ , Hong-Zhou Ye ₁ , Eric A Alt ₁ , Adam P Willard ₁ , Troy Van Voorhis ₁ , Stephen L Craig ₂ , Jeremiah A Johnson ₁

Affiliation

Photoresponsive materials that change in response to light have been studied for a range of applications. These materials are often metastable during irradiation, returning to their pre-irradiated state after removal of the light source. Herein, we report a polymer gel comprising poly(ethylene glycol) star polymers linked by Cu24 L24 metal-organic cages/polyhedra (MOCs) with coumarin ligands. In the presence of UV light, a photosensitizer, and a hydrogen donor, this "polyMOC" material can be reversibly switched between CuII , CuI , and Cu0 . The instability of the MOC junctions in the CuI and Cu0 states leads to network disassembly, forming CuI /Cu0 solutions, respectively, that are stable until re-oxidation to CuII and supramolecular gelation. This reversible disassembly of the polyMOC network can occur in the presence of a fixed covalent second network generated in situ by copper-catalyzed azide-alkyne cycloaddition (CuAAC), providing interpenetrating supramolecular and covalent networks.

中文翻译：

以香豆素修饰的 Cu24 L24 金属有机笼作为结点的聚合物网络介导的光切换溶胶-凝胶转变和催化作用。

人们已经研究了响应光而变化的光响应材料的一系列应用。这些材料在照射过程中通常是亚稳态的，在移除光源后恢复到照射前的状态。在此，我们报道了一种聚合物凝胶，其包含通过 Cu24 L24 金属有机笼/多面体（MOC）与香豆素配体连接的聚（乙二醇）星形聚合物。在存在紫外光、光敏剂和氢供体的情况下，这种“polyMOC”材料可以在 CuII 、 CuI 和 Cu0 之间可逆地转换。 CuI 和 Cu0 状态下 MOC 连接的不稳定性导致网络分解，分别形成 CuI /Cu0 溶液，该溶液在重新氧化为 CuII 和超分子凝胶化之前保持稳定。这种聚MOC网络的可逆分解可以在铜催化叠氮化物-炔环加成(CuAAC)原位产生的固定共价第二网络存在的情况下发生，从而提供互穿的超分子和共价网络。

更新日期：2020-01-16

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