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Abstract New tert -butylcarbazole modified β-diketone difluoroboron complexes CVB , PCVB , MPCVB and BPCVB have been synthesized. It was found that BPCVB without any traditional gelation group formed organogel in toluene, xylene, 1,3,5-triethylbenzene and 1,4-dioxane. The gained organogel and xerogel based on BPCVB gave a strong red fluorescence. The emission for the xerogel-based film was quenched by aniline vapor selectively, and the detection limit was as low as 2.0 ppb. It is interesting that the solid emission of the synthesized complexes was in the range of 600–850 nm, and the highest solid fluorescent quantum yield reached 0.37. These NIR dyes showed MFC behavior. For example, the as-synthesized sample of PCVB gave an emission band at 647 nm, and emitted red light under UV irradiation. The grinding of the as-synthesized sample resulted in the emitting color to turn to dark purple, accompanied with the red-shift of the emission to ca. 700 nm. The emission could recover to initial states by fuming the ground powders with CH 2 Cl 2 vapor. Based on the UV–vis spectra and XRD patterns in different solid-state for PCVB suggested that π-aggregates were formed in the as-synthesized crystals, and the grinding could destroy the aggregates and yield amorphous state. The transformation between crystalline and amorphous states led to MFC behavior. Graphical abstract Image 1 Highlights • New β-diketone difluoroboron complexes with high solid fluorescence quantum yields were synthesized. • BPCVB without any traditional gelation group formed organogels. • The xerogel-based film of BPCVB with red emission could detect gaseous aniline selectively. • These NIR dyes showed MFC behavior. [ABSTRACT FROM AUTHOR]

New difluoroboron β-ketoiminate boron complexes bearing benzoxazole ( CBO ) and benzothiazole ( CBS ) have been synthesized. It was found that CBO was almost non-emissive in THF, and the emission could be intensified significantly when great amount of H 2 O was added, illustrating AIE (aggregation-induced emission) property. CBS could not show AIE property in THF/H 2 O system, but its emission in solid state was also strong. The single crystal structure of CBS suggested that π-π interactions and the hydrogen bonds of C(Ar)−F⋅⋅⋅H, C(Ar)−H⋅⋅⋅S and C(Ar)−H⋅⋅⋅Cl would suppress the rotation of single bonds, resulting into obvious emission enhancement. It is interesting that the as-synthesized crystals of CBO and CBS both emitted azure light, and the grinding made their emitting colors to change into cyan and green, which could be recovered under fuming with DCM or heating. The reversible mechanofluorochromism was due to the transformation between crystalline and amorphous states, which could be confirmed from the results of absorption spectra, XRD patterns and DSC curves in different solid states. Additionally, the high-contrast mechanofluorochromism of CBS compared with CBO might be originated from the loose packing in crystalline state and the better π-electron delocalization. [ABSTRACT FROM AUTHOR]

New difluoroboron β-diketonate complexes functionalized with tert -butyl carbazole and carbazole ( TCBM and CBM ) have been synthesized, and they give strong emission in solid states with the fluorescence quantum yields of 0.63 and 0.99, respectively. Reversible mechanofluorochromic behaviors of TCBM and CBM are realized upon the treatment of grinding/fuming with CH 2 Cl 2 . Interestingly, the emitting colors of the annealed samples gained from the ground powders of TCBM depend on the heating temperature, and change from orange to yellow, yellowish green, and green with increasing temperature. The X-ray diffraction patterns illustrate that the transformation processes from crystalline structure to partial destroyed crystalline structure, till to amorphous state lead to the multi-color solid-state luminescence during thermofluorochromism. We deduced that tert -butyl can lead to the incompact packing of luminophores, which is more sensitive to external stimuli, so that multi-color solid-state luminescence can be afforded during mechanofluorochromic and thermofluorochromic processes. [ABSTRACT FROM AUTHOR]