Recyclable capture and release of iodine are crucial for environmental issues and the sustainable utilization of iodine. Herein, we present a linkage-engineering strategy in porous aromatic frameworks (PAFs) to regulate iodine adsorption and release. Three PAFs with identical tetraphenylmethane-triazine building blocks but featuring distinct linkages-carbon-carbon single bond (TPM-TTA), secondary amine (TPM-NTTA), and alkynyl group (TPM-ETTA)-demonstrate that the linkage type significantly influences framework properties, including structural defects, porosity, and hydrophilicity, which in turn determine iodine uptake capacity, adsorption kinetics, and recyclability. Among them, TPM-TTA exhibits the highest surface area of 1086 m2 g-1, and achieves the highest iodine uptake capacities from vapor (3.27 g g-1), saturated iodine aqueous solution (2.45 g g-1), and KI/I2 aqueous solution (6.93 g g-1), along with rapid, near-quantitative release in methanol. Notably, iodine-loaded TPM-TTA serves as a recyclable solid iodine reservoir, facilitating efficient iodine-mediated organic transformations, including β-iodoetherification of alkenes and α-sulfenylation of carbonyls, with broad substrate scope and excellent yields. This study highlights the rational linkage design as a powerful strategy to develop recyclable iodine adsorbents and further expands the practical applications of iodine-loaded materials in organic synthesis.
Keywords: iodine adsorption; linkage engineering; porous aromatic frameworks; α‐sulfenylation; β‐iodoetherification.
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