Twisted phenothiazine-terminated bisarylic methanone π-architecture exhibiting high-contrast mechanofluorochromism

Abstract

Bisarylic methanone π-architecture PTZ-BZ-DBT with carbonyl group as the acceptor and phenothiazine as the donor was synthesized. Theoretical calculations and photophysical properties in solution demonstrated that the obtained donor-acceptor (D-A) type molecule PTZ-BZ-DBT adopts a molecular conformation of high distortion and significant intramolecular charge transfer (ICT) behavior, which endows it not only with intense solid-state luminescence but also with a high-contrast mechanofluorochromic (MFC) feature. The original as-prepared samples of PTZ-BZ-DBT display bright yellow-green fluorescence. When the as-prepared samples are ground, the ground solid powders exhibit orange-red fluorescence are obtained. Accordingly, during the grinding process, the emission wavelength of the solid powders red shifts from 518 nm of the as-prepared samples to 617 nm of the ground samples, and thus a spectral shift of 99 nm is observed. Different from general MFC materials, if the ground solid powders are fumed by DCM vapor or annealed at 150 °C, the fluorescence peaks blue shift to about 564 nm, and the yellow-emitting Y-powders are gained. However, the ground samples can be converted into the as-prepared solid powders through solvent recrystallization; thus tri-color switching is obtained. The PXRD, fluorescence lifetimes, DSC and the spectral analysis demonstrate that the remarkable MFC nature of PTZ-BZ-DBT is attributed to crystalline-to-amorphous transition. Further, the red shift of the fluorescence band after grinding can be ascribed to the extension of conjugate length and subsequent planar intramolecular charge transfer (PICT) induced by conformational planarization under external forces.