Pressure-dependent distinct luminescent evolutions of pyrene and TPA-Py single crystals

The effects of the high pressure on two single crystals, pyrene and N,N-diphenyl-4-(pyren-1-yl)aniline (TPA-Py), were studied by in situ fluorescent and Raman spectroscopies. During the compression, the pyrene with one structureless excimer emission band showed a continuous bathochromic-shift. In contrast, with the pressure increasing to 10.36 GPa, TPA-Py previously dominated with the hybridized local and charge transfer (HLCT) excited state gradually exhibited a new band at longer wavelengths, which is assigned to a new excited state species with the intramolecular charge transfer (ICT) state, caused by the pressure-induced changes on its molecular configuration. Accompanied by the spectral changes, a sequential color variation from blue to cyan was observed, giving a change to yellow and then red. The significant broadening of the full-width half-maximum (FWHM) of the TPA-Py is observed due to the enhanced dipole-dipole interaction and the existence of pressure gradient. Both pyrene and TPA-Py showed the delayed recovery of the luminescence in the compression-decompression cycle, which results from the poor reversibility of electronic structure caused by the compression-induced piezochromic effect. Furthermore, the evolutions of the Raman spectra of pyrene and TPA-Py indicated that the pressure-induced reversible transformation is caused by the molecular conformational change. This study is a deeper understanding of the structure-property relation of the HLCT species and will be a helpful reference for the regulation of photoluminescence in these intramolecular electron donor-acceptor crystal materials.