Self-reversible mechanofluorochromism of AIE-active C6-unsubstituted tetrahydropyrimidine derivatives

The mechanofluorochromic properties of three C6-unsubstituted tetrahydropyrimidines (THPs), namely, diethyl 1,2,3-triphenyl-1,2,3,6-tetrahydropyrimidine-4,5-dicarboxylate (1), dimethyl 1,2,3-tri(4-trifluoromethylphenyl)-1,2,3,6-tetrahydropyrimidine-4,5-dicarboxylate (2), and dimethyl 1,2,3-tri(3-trifluoromethylphenyl)-1,2,3,6-tetrahydropyrimidine-4,5-dicarboxylate (3), with aggregation-induced emission (AIE) characteristics were investigated. The blue-green/cyan emissions of the three THPs can be switched reversibly by a grinding–fuming/heating process, with the change in maximum emission wavelength (λ(em)) up to 57 nm and the decrease of fluorescence quantum yields (Φ(F)). Interestingly, the green or cyan fluorescence of the ground powder (λ(em) is located at 481, 470 and 477 nm for 1b, 2 and 3, respectively) can spontaneously recover to the original blue (λ(em) is located at 434, 442 and 436 nm for 1b, 2 and 3, respectively) in 1–2 d at room temperature without any external stimulation. X-ray single-crystal diffraction, powder X-ray diffraction (XRD) and differential scanning calorimetry (DSC) studies demonstrate that the conversion between the molecular packing modes is the main reason for the mechanofluorochromism and the spontaneously recoverable mechanofluorochromism relates to intermolecular hydrogen bonds. The sensitively and/or spontaneously recoverable mechanofluorochromism of these THPs is expected to have great potential in sensing, optical recording and self-healing fluorescent materials.