Primary Structural Units “D+A–” Ion Pairs Dominating Near-Infrared Photothermal Conversion of Organic Ionic Cocrystals

The specific stacking mode of D/A blocks is often considered to largely determine the physicochemical properties of cocrystals. However, this rule may fail when encountering a large degree of (integer or near-integer) charge transfer situations. Herein, we explore the extensive correlations between the possible smallest structural units, stacking modes, and near-infrared photothermal conversion (NIR-PTC) properties of F4TCNQ-based cocrystals with typical features of integer-charge-transfer. Surprisingly, these cocrystals with distinct stacking modes display analogous D–A interactions, broad red-shift absorption, ultrafast (1–3 ps) relaxation dynamics of excited states, and excellent NIR-PTC properties. This supports that the resulting “D+A–” ion pairs from integer-charge-transfer may serve as the primary structural units beneath the secondary stacking modes to dominate the property of cocrystals. The stacking modes play an important but only secondary role. This work provides new insights into the structure–dynamics–property correlations and modular design of organic cocrystals for PTC and other applications.