Organic cocrystal engineering provides a promising route to promote the near-infrared (NIR) light harvesting and photothermal conversion (PTC) abilities of small organic molecules through the rich noncovalent bond interactions of D/A units. Besides, the single-bond rotatable groups known as "rotors" are considered to be conducive to the nonradiative transitions of the excited states of organic molecules. Herein, we propose a single-/double-bond dual-rotor strategy to construct D-A cocrystals for NIR PTC application. The results reveal that the cocrystal exhibits an ultra-broadband absorption from 300 nm to 2000 nm profiting from the strong π-π stacking and charge transfer interactions, and the weakened p-π interaction. More importantly, the PTC efficiency of cocrystals at 1064 nm in the NIR-II region can be largely enhanced by modulating the number of rotor groups and the F-substituents of D/A units. As is revealed by fs-TA spectroscopy, the superior NIR PTC performance can be attributed to the nonradiative decays of excited states induced by the free rotation of the single-bond rotor (-CH3) from the donors and the inactive double-bond rotor ([double bond, length as m-dash]C(C[triple bond, length as m-dash]N)2) being in the active form of [-C(C[triple bond, length as m-dash]N)2] in the excited states from the acceptors. This prototype displays a promising route to extend the functionalization of small organic molecules based on organic cocrystal engineering.
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