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Spirofluorene‐cored bis(difluoroboron β‐diketonate) complexes bearing terminal carbazoles (CbzBSF) and tert‐butylcarbazoles (TCbzBSF) have been synthesized. It was found that only TCbzBSF could form organogels in cyclohexane and methylcyclohexane, suggesting that tert‐butylcarbazole was essential for its organogelation directed by weak π–π interactions. It is worth noting that TCbzBSF could entrap ca. 5800 molecules of methylcyclohexane per gelator molecule, so this fully conjugated complex without traditional gelation group could be considered as a supergelator. The gained organogel showed reversible thixotropic and temperature‐dependent sol‐gel transitions. In particular, the orange red fluorescence of the xerogel‐based film of TCbzBSF could be quenched when exposed to gaseous aromatic amines of aniline, N‐methylaniline, and N,N‐dimethylaniline. The detection limit for aniline vapor of the xerogel‐based film was as low as 0.56 ppb. [ABSTRACT FROM AUTHOR]

Three linear push-pull compounds comprised of difluoroboron β-diketonate and triphenylamine unit 4,6-Bis(4-(diphenylamino)phenyl)-2,2-difluoro-2H-1,3,2-dioxaborinin-1-ium-2-uide, (E)-6-(4-(Diphenylamino)phenyl)-4(4(diphenylamino)styryl)-2,2-difluoro-2H-1,3,2-dioxaborinin-1ium-2-uide and 4,6-Bis((E)-4-(diphenylamino)styryl)-2,2-difluoro-2H-1,3,2-dioxaborinin-1-ium-2-uide (ABA, ABVA, and AVBVA) have been probed by many spectroscopies. The results clarify the photo-physical property of the compounds where ABVA and AVBVA are linked with vinyl units (V). The solvent-dependent steady absorption and photoluminescence spectra data shows that the vinyl unit and the polarity of the solvent influence the photo-physical properties of the compound. Moreover, the vinyl unit would further enhance the role of the polar environment. The transient absorption measurement then offers excitation relaxation behavior. The results show that excited compounds in cyclohexene go back to the ground state through the intramolecular charge transfer (ICT) state, and the transfer lifetime from the initial excited state to the ICT state would prolong after the introduction of vinyl unit. The relaxation behavior becomes complex when cyclohexene is replaced by tetrahydrofuran. Some excited compounds go directly back to the ground state and others go back to the ground state after passing through the ICT state. In addition, two-photon PL measurements and a Z-scan technique are employed, and this confirms that these compounds have two-photon behavior, but the two-photon absorption section gradually decreases. This decrease is attributed to the spectral shifting affected by the vinyl unit. [ABSTRACT FROM AUTHOR]

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]