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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 11 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