Mechanofluorochromic Properties of 1,4-Diphenylanthracene Derivatives with Hypsochromic Shift

Several types of 1,4-diphenylanthracene derivatives 1-4 were prepared, and their photophysical properties were observed in the solid and solution states. Interestingly, the CN-group-substituted 1,4-diphenylanthracene derivative 2 was found to exhibit a higher fluorescence quantum yield (ϕ_f = 0.71) in the solid state than in the solution state, probably due to the formation of an intermolecular Ar-CN⋯H-Ar hydrogen bond and antiparallel type locked packing structure in the solid state. Furthermore, for some derivatives, an increase in the fluorescence quantum yield was observed in the PMMA film (1 wt%) over both the solid state and the solution state. More interestingly, some of the 1,4-diphenylanthracene derivatives exhibited unusual mechanofluorochromic properties with a "hypsochromic shift" in luminous color depending on the substituents of the phenyl group, and with the derivatives having CF₃, OMe, CN, and two F substituents (1d-1f, 2-4) showing a significant luminous color change with a "hypsochromic shift" after grinding. However, no change in the luminous color was observed for the derivatives having H, Me, and one F substituent (1a-1c), and especially for some of the CN-substituted derivatives, a reversible luminous color change with a "hypsochromic shift" was observed, probably due to the formation of an antiparallel type packing structure. These "hypsochromic" anthracene derivatives could probably be utilized as new mechanofluorochromic materials.