Arene effects on difluoroboron beta-diketonate mechanochromic luminescence

Difluoroboron beta-diketonate (BF(2)bdk) dyes display reversible mechanochromic luminescence (ML) in the solid state. A series of BF2bdk dyes with methyl, phenyl, naphthyl and anthracyl groups (i.e. arene substituents and bdk ligands: Me-Ph mbm, Ph-Ph dbm, Np-Ph nbm, An-Ph = abm) were prepared to test the effects of p conjugation length and arene size on ML properties. Solid-state emission spectra were recorded for powders, spin-cast films, and dye coated weighing paper. The materials emit at various wavelengths from blue to red, depending on the conjugation length. Additionally, emission spectra were recorded for smeared solids and their recovery was tracked at room temperature over time. All dyes except for BF(2)mbm show emission changes upon mechanical perturbation, with increasing pi conjugation correlating with more dramatic, redshifted fluorescence, however, their recovery is significantly affected by the aromatic substituents. The thermal and structural properties of the dyes in the solid state were also investigated by differential scanning calorimetry (DSC) and atomic force microscopy (AFM).