Reversible luminescence color switching in the crystal polymorphs of 2,7-bis(2′-methyl-[1,1′-biphenyl]-4-yl)-fluorenone by thermal and mechanical stimuli

Abstract

Smart organic luminescence materials that exhibit a reversible stimuli-responsive change of luminescence color in the solid state without changing the chemical structure of their component molecules have attracted increasing interest. We employed the design strategy of introducing different weak interactions into the same molecular system to synthesize 2,7-bis(2′-methyl-[1,1′-biphenyl]-4-yl)-fluorenone (MPF). Two crystal polymorphs of MPF, green-yellow crystal G-MPF and orange crystal O-MPF, were obtained through culturing the single crystal under the different crystallization conditions of diffusing diethyl ether into its respective tetrahydrofuran or CH₂Cl₂ solution. Both of the two crystal polymorphs exhibit high luminous efficiency and reversible stimuli-responsive solid-state luminescence color switching. Upon heating the green crystal G-MPF or grinding the orange crystal O-MPF, their emission reversibly changes between green at 530 nm and orange at 570 nm. The X-ray single-crystal structures, characterization of the photophysical properties, powder X-ray diffraction and differential scanning calorimetry provide insight into the phase transformation and the luminescence behavior. The results indicate that the green emission of G-MPF originates from molecular J-aggregation and the orange emission of O-MPF originates from static excimers. This work discusses the relationship between the molecular stacking mode and the photophysical properties, and demonstrates a molecular design strategy to obtain stimuli-responsive organic solid-state luminescence switching materials.