Highly Efficient Construction and in Situ Post‐Assembly Modification of Multifunctional Metal–Organic Cages in Microdroplets
Abstract
Abstract Confined microenvironments provide a powerful platform for guiding supramolecular self‐assembly, analogous to intracellular environments that drive key biological processes. Nevertheless, the construction and post‐assembly modification of multifunctional metal–organic cages (MOCs) within microdroplets remains a significant challenge. Here, we present a microdroplet‐based strategy for the rapid and efficient synthesis of structurally diverse tetrahedral MOCs, incorporating functionalities such as aggregation‐induced emission and photosensitization. Compared with batch reactors, reactions in microdroplets led to dramatically accelerated self‐assembly. More importantly, we report the first example of post‐assembly functionalization of MOCs within microdroplets, achieved through azide–cyclooctyne click chemistry, enabling the incorporation of twelve BODIPY chromophores to generate multifunctional cages integrating both photosensitizing and fluorescence functionalities. The confined droplet milieu not only facilitated the self‐assembly but also enhanced the subsequent modification processes. The functionalized MOCs demonstrated markedly enhanced photocatalytic activity within microdroplets, achieving turnover frequencies up to forty times higher than those obtained in batch reactors in the synthesis of the pharmaceutically relevant quinone juglone. Collectively, this study establishes microdroplet reactors as powerful biomimetic platforms for the rapid and precise construction, functionalization, and application of supramolecular architectures.
Article Details
Authors (12)
Pei‐Pei Jia
State Key Laboratory of Petroleum Molecular & Process Engineering Shanghai Key Laboratory of Green Chemistry and Chemical Processes Shanghai Frontiers Science Center of Molecule Intelligent Syntheses Liwa Institute of Skin Health, Wuhu Hospital Affiliated to East China Normal University, School of Chemistry and Molecular Engineering East China Normal University Shanghai 200062 P. R. China
Lu Rao
State Key Laboratory of Petroleum Molecular and Process Engineering, Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering
Danyang Hong
State Key Laboratory of Petroleum Molecular & Process Engineering Shanghai Key Laboratory of Green Chemistry and Chemical Processes Shanghai Frontiers Science Center of Molecule Intelligent Syntheses Liwa Institute of Skin Health, Wuhu Hospital Affiliated to East China Normal University, School of Chemistry and Molecular Engineering East China Normal University Shanghai 200062 P. R. China
Tongyuan Wu
State Key Laboratory of Petroleum Molecular & Process Engineering Shanghai Key Laboratory of Green Chemistry and Chemical Processes Shanghai Frontiers Science Center of Molecule Intelligent Syntheses Liwa Institute of Skin Health, Wuhu Hospital Affiliated to East China Normal University, School of Chemistry and Molecular Engineering East China Normal University Shanghai 200062 P. R. China
Jian Yu
Department of Chemistry
Changyin Yang
State Key Laboratory of Petroleum Molecular & Process Engineering Shanghai Key Laboratory of Green Chemistry and Chemical Processes Shanghai Frontiers Science Center of Molecule Intelligent Syntheses Liwa Institute of Skin Health, Wuhu Hospital Affiliated to East China Normal University, School of Chemistry and Molecular Engineering East China Normal University Shanghai 200062 P. R. China
Yi‐Xiong Hu
State Key Laboratory of Petroleum Molecular & Process Engineering Shanghai Key Laboratory of Green Chemistry and Chemical Processes Shanghai Frontiers Science Center of Molecule Intelligent Syntheses Liwa Institute of Skin Health, Wuhu Hospital Affiliated to East China Normal University, School of Chemistry and Molecular Engineering East China Normal University Shanghai 200062 P. R. China
Xiao Luo
Wei‐Tao Dou
State Key Laboratory of Petroleum Molecular & Process Engineering Shanghai Key Laboratory of Green Chemistry and Chemical Processes Shanghai Frontiers Science Center of Molecule Intelligent Syntheses Liwa Institute of Skin Health, Wuhu Hospital Affiliated to East China Normal University, School of Chemistry and Molecular Engineering East China Normal University Shanghai 200062 P. R. China
Xuhong Qian
State Key Laboratory of Bioreactor Engineering, Shanghai Key Laboratory of Chemical Biology, School of Pharmacy, East China University of Science and Technology, Meilong Road 130, Shanghai 200237, China
Hai‐Bo Yang
School of Chemistry and Molecular Engineering East China Normal University Shanghai China
Lin Xu
Harold C. Simmons Comprehensive Cancer Center, University of Texas Southwestern Medical Center, Dallas, TX, USA.