Dual Charge Transfer Generated from Stable Mixed-Valence Radical Crystals for Boosting Solar-to-Thermal Conversion

Realizing dual charge transfer (CT) based on stable organic radicals in one system is a long-sought goal, however, remains challenging. In this work, a stable mixed-valence radical crystal is designed via a surfactant-assisted method, namely TTF-(TTF^+• )₂ -RC (where TTF = tetrathiafulvalene), containing dual CT interactions. The solubilization of surfactants enables successful co-crystallization of mixed-valence TTF molecules with different polarity in aqueous solutions. Short intermolecular distances between adjacent TTF moieties within TTF-(TTF^+• )₂ -RC facilitate both inter-valence CT (IVCT) between neutral TTF and TTF^+• , and inter-radical CT (IRCT) between two TTF^+• in radical π-dimer, which are confirmed by single-crystal X-ray diffraction, solid-state absorption, electron spin resonance measurements, and DFT calculations. Moreover, TTF-(TTF^+• )₂ -RC reveals an open-shell singlet diradical ground state with the antiferromagnetic coupling of 2J = -657 cm^-1 and an unprecedented temperature-dependent magnetic property, manifesting the main monoradical characters of IVCT at 113-203 K while the spin-spin interactions in radical dimers of IRCT are predominant at 263-353 K. Notably, dual CT characters endow TTF-(TTF^+• )₂ -RC with strong light absorption over the full solar spectrum and outstanding stability. As a result, TTF-(TTF^+• )₂ -RC exhibits significantly enhanced photothermal property, an increase of 46.6 °C within 180 s upon one-sun illumination.