Organic cocrystal exhibits excellent photothermal conversion (PTC), but how the intermolecular interactions of cocrystals regulate the PTC is obscure. Here, two isomeric donor molecules (phenanthrene and anthracene) and two electron-withdrawing molecules (7,7,8,8,8-tetracyanodimethylquinone and 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinone dimethane) are self-assembled into the four cocrystals (PTQ, PFQ, ATQ, and AFQ). By changing the molecular configuration of the donor and the electron-withdrawing ability of the acceptor, the intrinsic influencing factors of the intermolecular interaction on the PTC were explored. Under near-infrared laser (808 nm) irradiation, the PTC efficiencies of PTQ, PFQ, AFQ, and ATQ are 35.85, 44.74, 57.00, and 60.53%, respectively. Based on the single-crystal X-ray diffraction, ultrafast time-resolved transient absorption, and excited-state theoretical calculations, we found that the π-π stacking in ATQ and AFQ is conducive to promoting the near-infrared light-harvesting ability and the p-π interaction of cocrystals can regulate the nonradiative rotation of -C(C≡N)2 groups, resulting in a tunable near-infrared PTC via the isomeric cocrystals. Accordingly, the evaporation rate of the porous polyurethane-AFQ foam can reach 1.33 kg·m-2·h-1 in the simulated solar-driven water evaporation system. This work provides a strategy to boost the PTC by the intermolecular interactions of cocrystal materials.
Keywords: cocrystal; excited state; femtosecond transient absorption; isomer; near-infrared photothermal conversion; nonradiative process; solar-driven water evaporation.