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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]

Novel luminescent organogelators based on nucleoside functionalized with carbazole (UC8, UC12 and UC16) were designed and synthesized. Their gelation ability was tested and it was found that both UC12 and UC16 could form stable organogels in toluene/petroleum ether. The UV-vis absorption, fluorescence emission and IR spectral changes during the gelation of UC12 proved that the self-assembly was driven by H- bonding. The morphology of the xerogel UC16 obtained from toluene/petroleum ether (v/v = 1/1) displayed tough rod-like microstructures, and 3D networks formed from lots of nanofibers were observed for the xerogel UC16 obtained from toluene/petroleum ether (v/v = 2/1). It was interesting that the obtained organogels emitting blue light could be destroyed by the addition of F-, accompanied with the declining the emission intensity. Therefore, these organogels could be used as sensory materials to recognize F-. [ABSTRACT FROM AUTHOR]

We have synthesized a series of new β-iminoenolates and their corresponding difluoroboron complexes without any traditional gelation moieties, and some of them were able to gelatinize organic solvents. It was found that the presence of halogen atoms as substituents had a significant effect on gelation ability. In particular, bromo-containing compounds 4 A and 4 B exhibited excellent gelation abilities compared with other halogen-substituted gelators. By analyses of the single-crystal structure, the PXRD pattern of the xerogel, and electronic spectral changes during gelation, we deemed that π-π, C−H⋅⋅⋅F, and C−H⋅⋅⋅Br interactions were the driving forces for the gelation of 4 B. Interestingly, ( Z)-1-(4-bromophenyl)-2-(3-methylpyrazin-2-yl)ethen-1-ol ( 8 A), prepared in this work, is the lowest-molecular-weight organogelator to have been reported. It should be noted that although β-iminoenolates 3 A- 5 A are nonemissive in solution, they emit strong yellow light in organogels, which suggests aggregation-induced emissive activity, whereas the difluoroboron complexes 3 B- 5 B show strong fluorescence in solutions, organogels, and xerogel-based films. Moreover, we found that the emission of 4 B in a nanofiber-based film could be quenched significantly upon exposure to gaseous trifluoroacetic acid and that the decay time and detection limit were 0.5 s and 0.17 ppm, respectively. Thus, through this work we have provided a new strategy for the design of nontraditional π gelators by introducing halogen atoms into π-conjugated systems with moderate polarities. [ABSTRACT FROM AUTHOR]

New carbazole modified salicylaldimine derivatives 1a–3a and their difluoroboron complexes 1b–3b were synthesized. It was found that 3a and 3b bearing both tert-butyl and trifluoromethyl could form stable gels in some organic solvents, while no gel could be formed from 1a–1b and 2a–2b without tert-butyl or trifluoromethyl, respectively. It suggested that both tert-butyl and trifluoromethyl played key roles in the gel formation because they could tune the solubility of the compounds and adjust the strength of intermolecular interactions. It should be noted that there is no traditional gelation moiety involved in gelators 3a and 3b. The main driving force for the gelation of such nontraditional π-gelators was π–π interaction. Meanwhile, aggregation-induced emission (AIE) was detected during the organogelation process of 3a, and the gel–sol transition took place upon adding F−. Interestingly, complexes 1b and 3b exhibited reversible piezofluorochromic (PFC) behaviors upon grinding/fuming, which originated from the transformation between crystalline and amorphous states. Herein, we provided a new strategy for designing new stimuli-responsive multifunctional soft materials. [ABSTRACT FROM AUTHOR]

Nanofibers based on phenanthroimidazole derivatives PCC, PDC, and PSC were fabricated by organogelation processes, and their fluorescence sensory properties towards acid were investigated. It was found that the emission of PCC in the nanofiber-based film could be quenched significantly upon exposure to gaseous TFA due to the formation of protonated PCC, in which ICT (intramolecular charge transfer) would occur. On the other hand, TFA vapor led to the emitting colors of PDC and PSC in the nanofiber-based films to turn to yellow and green from sky blue and blue, respectively. Additionally, we found that the decay times of PCC were 0.1 s and 1.9 s in probing the saturated vapor of TFA in nanofiber-based film and in spin-coated film, respectively. The results suggested that the high surface-to-volume ratio and large interspace in the nanofiber-based networks favored the enhanced adsorption, accumulation, and diffusion of gaseous molecules, resulting in such a high performance. [ABSTRACT FROM AUTHOR]

A glutamide gelator, 1, was synthesized,and a weakemission enhancement was observed during its gelation. In addition, 1could be an excellent scaffold for successfully embeddingan energy acceptor, 2, into its aggregate to obtain highlyefficient energy transfer. An amplification of the emission enhancementwas observed in the two-component gels compared to that of the neatgel of 1during gel formation. For example, 1induced only a 2.5-fold increase in emission intensity, whereasa 23-fold enhanced emission could be observed in the two-componentgel with only 1.6 mol % 2. Furthermore, two-componentgels had an excited proton response. In systems with low acceptorconcentrations, the hot solution red-shifted the fluorescence fromblue to yellow upon the addition of a proton, which continuously blue-shiftedwith decreasing temperature to form the gel given that the bindingof the gelator to the proton is weakened during coassembly. Moreover,the casting film formed by the two-component wet gel had an excellentresponse to volatile acids such as hydrochloric acid, trifluoroaceticacid, and so on and could be reversibly recovered by exposure to NH3. [ABSTRACT FROM AUTHOR]

Abstract: Copper sulfides were synthesized by using the low-molecular-mass hydrogel nanofibers self-assembled from a L-glutamic acid derivative. The as-prepared copper sulfides showed a nanoribbon structure with diameter of 30–70nm and lengths of 1–10μm. The investigation of FT-IR absorption spectra and XRD pattern for the neat hydrogel and composite gel suggested that H-bonding was the main driving force to help the formation of ordered nanofibers of the hydrogel and the composite gel. The resulted mineralization indicated that the inorganic ions (Cu2+) were firstly coordinated to the carboxylate anions (COO−). With the penetration of H2S, the preformed CuS nanoparticles on the surface of the fibers acted as the growing points for the continuous growth. [Copyright &y& Elsevier]

Rigid boomerang shaped triphenylamine functionalized bis-β-diketone-boron difluoride without alkyl chain and H-bonding unit exhibits good gelation ability in some mixed organic solvents directed by optimally balanced π–π interactions. [ABSTRACT FROM AUTHOR]

The first rigid dendritic gel with strong emission based on oligocarbazole was reported. It is interesting that the second generation of dendron exhibited gelation ability under ultrasound, and two-component gel could be formed from the first generation of dendron assisted by 1,6-diaminohexane. [ABSTRACT FROM AUTHOR]

Abstract: Two-component organogelators based on a discotic H-bonding donor of 1,3,5-tris(4-amidobutanoic acid)phenyl benzene (2), and acceptors of 4-(4-alkoxybenzoyloxy)-4′-stilbazole derivatives were reported. These complexes showed good gelation ability for alcohols, which are known to be unfavorable for H-bonding formation. SEM study revealed that sheet-like network, nanotapes, and nanorods were gained from the self-assembling of the complexes with small difference of the carbon chain length. Based on XRD, IR, temperature-dependent 1H NMR, and UV–vis absorption investigations, the gel-phase materials were generated from 1D columnar-type packing of complexes facilitated by cooperative H-bonding, π-stacking, and van der Walls interactions. [Copyright &y& Elsevier]

Abstract: We report on the synthesis and self-assembly of a new discotic organogelator based on π-conjugated triphenylbenzene with three peripheral chiral substituents. It is found that the introduction of chiral groups to the C 3-symmetric molecule led to a hexagonal columnar chiral stacking of the molecules in a clockwise direction in the organogel fibers. And the fluorescent emission of the gel decreased significantly compared to the monomer state at the same concentration, as a result of the aggregation of the nonplanar triphenylbenzene core in the gel phase. [Copyright &y& Elsevier]

Four fluorescent low molecular weight gelators based on benzoxazole or benzothiazole functionalized pyrimidine were designed and synthesized. The ability of the target was tested, and all compounds could form stable supramolecular gels in an alcohol/water mixture and its fluorescence increased during gel formation. Photophysical spectra during gel formation, SEM, XRD, FT-IR study suggested that the self-assembly was driven by hydrogen bonding, van der Waals forces and weak π-π interaction. Interestingly, the gel collapsed after being illuminated by 365 nm UV light and 1H NMR of the gel before and after illumination proved that the [2 + 2]-cycloaddition between the double bond of pyrimidine was responsible for the light response. Furthermore, the fluorescent of xerogel film could be quenched by volatile acids while the fluorescent of the solution was enhanced after acid was added. The different phenomena were discussed. The nano-fiber assembled via gel formation could be used as fluorescent imaging material of latent fingerprints. [Display omitted] • Design and synthesis of novel uracil derivatives containing benzoxazole and benzothiazole. • Benzoxazole-modified uracil derivatives exhibit good gelation abilities and driving force of gel formation was investigated. • The gel could respond to light and acid. The response mechanism was studied. • The nano-materials assembled via gel formation could be used as fluorescent imaging material of latent fingerprints. [ABSTRACT FROM AUTHOR]

Four cyanostyryl-substituted carbazole derivatives (CN-ODEC1, CN-ODEC2, CN-DDEC1, and CN-DDEC) were synthesized and their self-assembly properties have been studied. It was found that they could form organogels especially in aromatic solvents. Scanning electron microscopy and light microscopy images show that the xerogels formed from monosubstituted derivatives (CN-O/DDEC1) gave well-organized tapes, and those from disubstituted derivatives (CN-O/DDEC2) exhibited heavy entangled three-dimensional structures. The UV–vis absorption and fluorescence emission spectra, as well as X-ray diffraction patterns, suggest that carbazole derivatives underwent J-type π-stacking. Meanwhile, we suggested that strong H-bonding and moderate π–π interactions were the key driving force for the gelation of the monosubstituted derivatives, and head-to-tail “ladder-type” J-aggregates were formed in the gel state. On the other hand, strong π–π interaction might be considered as the main driving force for the gelation of disubstituted derivatives, and J-aggregates with no well-organized packing mode of molecules were obtained in the gel phase. It should be noticed that aggregation-induced emission was observed during the gelation processes. [ABSTRACT FROM AUTHOR]

New β-diketone-boron difluoride complexes functionalized with tetraphenylethene ( TPEB , DTPEB and TTPEB ) which exhibit AIE (aggregation-induced emission) properties have been synthesized. It was found that only boomerang-shaped DTPEB without any traditional gelation groups could form organogel in specific organic solvents. It gave strong orange red fluorescence in organogel as well as in xerogel-based film although it was non-emissive in solution. It is interesting that the emission of DTPEB in xerogel-based film could be quenched significantly upon exposure to triethylamine (TEA) vapour, and the detection limit was as low as ca. 0.1 ppb. This work provides a strategy for the synthesis of a new rigid non-traditional π-gelator via the construction of a boomerang-shaped π-conjugated skeleton. In addition, the gelation of the π-gelators with AIE ability is a facile method for the fabrication of luminescent organic nanomaterials. [ABSTRACT FROM AUTHOR]

New triphenylvinyl substituted carbazole derivatives TPEICE , TPEC and TPECBr have been synthesized. They could self-assemble into nanofibers via organogelation processes in some organic solvents. Notably, the obtained xerogel-based films could emit strong fluorescence although the three compounds were non-emissive in solutions, indicating AIE in gel phases. The emission of TPEICE and TPEC in xerogel-based films could be quenched significantly upon exposed to gaseous DNT and TNT, while TPECBr could not sense nitro compounds on account of its poor electron donating ability. We also found that reversibility of the fluorescence response of TPEC was better than TPEICE because the photo-induced electron transfer would happen during the recognition of nitroaromatics for TPEICE and TPEC , except for the formation of charge–transfer complex between TPEICE and nitro compounds. Therefore, the different fluorescence response behaviors of TPEICE , TPEC and TPECBr towards nitroaromatics were resulted from their different electron donating abilities. [ABSTRACT FROM AUTHOR]

Four new D-π-A type N,O -chelated BF 2 complexes (TCBOB , TCBTB , TCQB and TCPB) were synthesized. It was found that TCPB bearing the ligand of N -(1-pyridinyl)benzoamide shows gelation ability in methylcyclohexane, DCM/peteroleum ether, etc. The time-dependent UV–vis absorption and fluorescent emission spectral changes during the gel formation revealed that π-π interactions play important roles in the self-assembling processes. Particularly, the emission of the xerogel-based film of TCPB can be quenched by TFA (trifluoroacetic acid) vapor, and it showed high performance in the detection of TFA compared with the spin-coating films of TCBOB , TCBTB and TCQB. In addition, the BF 2 complexes exhibited reversible mechanofluorochromic behavior under the treatment of grinding/fuming or heating, and TCPB gave high-contrast mechanofluorochromism compared with others. XRD patterns in different solid states demonstrated that the external mechanical forces can induce the transformation from the crystalline to the amorphous states. Powder of TCPB was also used to image latent fingerprints on surface of glasses, and distinct fluorescent images were obtained. [Display omitted] • New BF 2 complexes were synthesized. • Gelation abilities and MFC properties of them were studied. • They were first used to detect LFP. [ABSTRACT FROM AUTHOR]