Supramolecular free radicals: near-infrared organic materials with enhanced photothermal conversion† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c5sc01167a

A novel kind of supramolecular free radical with significantly improved free radical yield and enhanced near-infrared (NIR) photothermal conversion has been fabricated. Perylene diimide (PDI) can undergo chemical reduction to generate PDI radical anions. Cucurbit[7]uril (CB[7]), a bulky hydrophilic head, was utilized to encapsulate the two end groups of the PDI derivative via host-guest interactions, thus hindering its aggregation and suppressing the dimerization and quenching of PDI radical anions in aqueous solution. Due to the increased concentration of radical anions and their absorption above 800 nm, the efficiency of NIR photothermal conversion was significantly improved. Compared with free radicals fabricated by covalent chemistry, the supramolecular free radicals established here could provide a facile approach for the promoted formation of aromatic free radicals, thus opening up a new strategy for the design of NIR photothermal materials with enhanced photothermal conversion.