Design and synthesis of dicyanoethylene derivatives functionalized with carbazole possessing the properties of obvious aggregation-induced emission and reversible high-contrast mechanofluorochromism

This study devotes to the design, preparation, and examination of two novel D-A structured molecules, designated as CCEDBF and BCCEDBF, which are derived from carbazole unit, dicyanoethylene segment, and dibenzofuran unit. The distinctive D-A molecular architectures and highly twisted spatial configurations of these compounds facilitate pronounced intramolecular charge transfer (ICT) while also imparting robust solid-state luminescence, exhibiting emission efficiencies of 0.518 and 0.739, respectively, and notable aggregation-induced emission (AIE) with AIE factors of 43 and 30. Significantly, both CCEDBF and BCCEDBF demonstrate reversible mechanofluorochromic (MFC) behavior characterized by high fluorescence contrast. Mechanical grinding of the initial powders results in a shift in their emission colors, transitioning from green and yellow-green to yellow and orange-red, respectively, alongside a corresponding shift in emission peaks from 525 nm to 536 nm–558 nm and 597 nm. Powder X-ray diffraction (PXRD) examination of the initially synthesized, mechanically processed, and vaporized samples reveals that the observed fluorescence color change is due to a structural transformation between ordered crystalline and disordered amorphous configurations induced by the application of the external force. The red shift in photoluminescence (PL) spectra post-grinding is attributed to a reduced band gap, driven by factors such as extended π-conjugation length, enhanced planar intramolecular charge transfer (PICT) effect, strengthened π-π interactions and exciton coupling, as well as the increase in the orbitals overlap between neighboring molecular. Moreover, the presence or absence of tert-butyl substituents attaching to the 3- and 6-positions of the carbazole units significantly impacts the photophysical properties of these materials.