Highly Luminescent TCNQ in Melamine

Optical properties of molecules change drastically as a result of interactions with surrounding environments as observed in solutions, clusters, and aggregates. Here, we make 7,7,8,8-tetracyanoquinodimethane (TCNQ) highly luminescent by encapsulating it in crystalline melamine. Colored single crystals are synthesized by slow evaporation of aqueous tetrahydrofuran solutions of melamine and TCNQ. Single-crystal X-ray diffraction reveals the lattice structure of pure melamine, meaning that the color is of impurities. Both mass spectrometry and UV-vis spectroscopy combined with density-functional theory calculations elucidate that the impurity species are neutral TCNQ and its oxidation product, dicyano-p-toluoyl cyanide anion (DCTC^-), whose concentrations in a melamine crystal can be controlled by adjusting the molar ratio between melamine and TCNQ in the precursor solution. Fluorescence excitation-emission wavelength mappings on the precursor solutions illustrate dominant emissions from DCTC^- while the emission from TCNQ is quenched by the resonance energy transfer to DCTC^-. On the contrary, TCNQ in crystalline melamine is a bright fluorophore whose emission wavelength centered at 450 nm with internal quantum yields as high as 19% and slow fluorescence lifetimes of about 2 ns. The method of encapsulating molecules into transparent melamine would make many other molecules fluorescent in solids.