Unprecedented Improvement of Near-Infrared Photothermal Conversion Efficiency to 87.2% by Ultrafast Non-radiative Decay of Excited States of Self-Assembly Cocrystal

-phenylenediamine (TMPD) and pyromellitic dianhydride (PMDA)) with strong absorption in NIR range is constructed, with widespread absorption (200-1500 nm) and very high NIR photothermal conversion efficiency (87.2%). Essentially, in this cocrystal, a small HOMO-LUMO gap of donor-acceptor pair boosts the absorption ability of this cocrystal in the NIR range. The mixed stacking structure significantly enhances the intermolecular interactions as well as the electron-hole delocalization, suppressing the emission processes, leading to nonradiative decay processes from excited states. Strong intermolecular interactions enable the cocrystal to have dense electronic energy levels, leading to a high proportion (94.4%) vibrational cooling and internal conversion processes with ultrafast excited-state relaxation (0.12 ps), which contributes to high NIR photothermal conversion efficiency. Furthermore, the cocrystal has exhibited capable ability for being an excellent candidate for a NIR photothermal therapy agent.