Developing a general, facile, and direct strategy for synthesizing thin films of covalent organic frameworks (COFs) is a major challenge in this field. Herein, we report an unprecedented electrocleavage synthesis strategy to produce imine-linked COF films directly on electrodes from electrolyte solutions at room temperature. This strategy enables the cathodic exfoliation of the COF powders to nanosheets by electrochemical reduction and protonation, followed by nanosheets migrating to the anode and reproducing the COF structures by anodic oxidation. Our method is adaptable with most imine-linked COFs by virtue of the low redox potential of the imine bonds, whereas the COF films possess high crystallinity and hierarchical porosity. We highlight these COF films as a superb platform for promoting mass transfer by demonstrating their extraordinarily rapid iodine adsorption with record-high rate constants.
In expanding our research activities of superlattice engineering, designing new giant molecules is the necessary first step. One attempt is to use inorganic transition metal clusters as building blocks. Efficient functionalization of chemically precise transition metal clusters, however, remains a great challenge to material scientists. Herein, we report an efficient thiol‐Michael addition approach for the modifications of cyclic titanium‐oxo cluster (CTOC). Several advantages, including high efficiency, mild reaction condition, capability of complete addition, high atom economy, as well as high functional group tolerance were demonstrated. This approach can afford high yields of fully functionalized CTOCs, which provides a powerful platform for achieving versatile functionalizations of precise transition metal clusters and further applications.
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