Highly Luminescent TCNQ in Melamine

Author(s)
Vipin Mishra, Arthur Mantel, Peter Kapusta, Alexander Prado-Roller, Hidetsugu Shiozawa
Abstract

Optical properties of molecules change drastically as results of interactions with surrounding environments as observed in solutions, clusters and aggrergates. Here we make 7,7,8,8-tetracyanoquinodimethane (TCNQ) highly luminescent by encapsulating it in crystalline melamine. Coloured single crystals are synthesized by slow evaporation of a solution of melamine and TCNQ in water and tetrahydrofuran. Single crystal X-ray diffraction reveals the lattice structure of pure melamine, meaning that the colour 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 exciation-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 and slow fluorescence lifetimes of about 2 ns. Our method of encapsulating molecules into transparent melamine would make many other molecules fluorescencent in solids.

Organisation(s)
Core Facility Crystal Structure Analysis, Department of Inorganic Chemistry, Electronic Properties of Materials
External organisation(s)
Czech Academy of Sciences
Journal
ACS Applied Optical Materials
Volume
2
Pages
1128–1135
No. of pages
8
ISSN
2771-9855
DOI
https://doi.org/10.26434/chemrxiv-2023-945vj
Publication date
08-2023
Peer reviewed
Yes
Austrian Fields of Science 2012
103018 Materials physics
Keywords
Portal url
https://ucrisportal.univie.ac.at/en/publications/533a7c9c-7eb0-4fe2-9a57-e258a63302f4