In this work, we report a detailed investigation on the factors affecting the in-plane motion of tetrafluoro-1,4-benzoquinone (TFBQ) within a series of charge-transfer (CT) cocrystals formed with various fused aromatic donors. Six crystalline materials were obtained, including four cocrystals, a polymorph, and a solid solution. These were characterized by single-crystal X-ray diffraction (SC XRD), solid-state NMR, FTIR, UV-Vis spectroscopy, and DFT calculations. All cocrystals exhibited short π-stacking interactions and varied noncovalent interactions (NCI) modulating the in-plane motion of TFBQ. 19F T₁ relaxation measurements allowed the quantification of the activation enthalpies (ΔH‡) and entropies (ΔS‡), with theoretical calculations backing these results. Cocrystal 4 is the solid with the most restricted motions due to the presence of strong hydrogen bonds. In contrast, cocrystal 3a depicts the highest in-plane motional frequencies (up to 2.2 MHz at 300 K), owing to the weak contacts around TFBQ. Surprisingly, a solid solution (5), which resembled a mixture of cocrystals 2 and 3a, displayed no significant in-plane motions, despite having similar packing and relaxation behavior to the binary cocrystals. This work illustrates how subtle variations in donor structure affect the in-plane motions and photophysical properties of CT cocrystals, providing valuable insight into the rational design of functional materials.

Institute of Organic Chemistry and Biochemistry Czech Academy of Sciences Prague 160 00 Czech Republic

Instituto de Química Universidad Nacional Autónoma de México Circuito Exterior S N Ciudad Universitaria Coyoacán 04510 Mexico

Research Group of Optical Properties of Materials Centro de Investigaciones en Óptica CIO Apdo Postal 1 948 León Guanajuato 36700 Mexico

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