Molecule Recognition and Release Behavior of Naphthalenediimide Derivative via Supramolecular Interactions

Self-assembled charge-transfer complexes based on supramolecular interactions have attracted immense research interest due to their unique packing and (opto)electronic applications. Herein, two new binary cocrystals with a similar 1:1 mixed-stack arrangement are synthesized by solvent evaporation or grinding method using N,N′-dimethyl-1,4,5,8-naphthalene tetracarboxylic diimide (Me-NDI) as the receptor. Single-crystal X-ray diffraction analysis confirms the successful molecular-level recognition and various weak interaction networks. Upon thermal treatment of 1,4,8,11-tetramethyl-6,13-triethylsilylethynyl pentacene (TMTES-P)/Me-NDI complex, in situ cocrystal-to-crystal conversion is observed, and the receptor is gradually released, while the perylene/Me-NDI cocrystal disassembles in the same manner as a single-component compound. The aligned short-contact network, good stability of TMTES-P, and anisotropic attachment energies of the TMTES-P/Me-NDI cocrystal disassemble in a manner same to that of a single-component compound. The aligned short-contact network, good stability of TMTES-P, and anisotropic attachment complexes are believed to promote the release of specific molecules. These structure–property relationship results provide new insights into the design of a supramolecular class with desired functionalities in terms of self-assembled recognition, release, or crystal conversion.