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Four new D-π-A-type difluoroboron β-carbonyl cyclic ketonate complexes that contain carbazole units ( TCCH, TCCP, CCH, and CCP) have been synthesized that exhibited reversible mechanofluorochromic (MFC) behaviors. Interestingly, TCCH and TCCP, which contained a tert-butyl carbazole group, exhibited high-contrast mechanofluorochromism compared with CCH and CCP, which just contained a carbazole group. For example, shifts of Δ δ=49 and 20 nm were detected during the mechanofluorochromism of TCCH and CCH, respectively. We found that tert-butyl carbazole derivatives existed as isolated molecules in the as-synthesized crystals, on account of the steric hindrance of the tert-butyl groups, and that J-aggregates were formed upon grinding. Transformation between the isolated and aggregated molecules, which was stimulated by mechanical force, led to clear changes in the emission properties. However, J-aggregates were formed in the as-synthesized crystals of carbazole derivatives, and grinding only weakened the strength of the π-π interactions, thereby resulting in low-contrast mechanofluorochromism. Therefore, this approach provides a useful strategy for the design of MFC dyes with high performance. [ABSTRACT FROM AUTHOR]

We have synthesized a series of salicylaldimine difluoroboron complexes that contain carbazole moieties. Substituents on the carbazole and on the benzene rings of the salicylaldimine moiety influenced the intramolecular charge transfer (ICT) emissions of these complexes. Interestingly, the synthesized difluoroboron complexes emitted strong light in the solid state under UV irradiation and exhibited reversible mechanofluorochromism behavior. The emission of a pristine sample of 3-[4-(3,6-di- tert-butyl-9 H-carbazol-9-yl)phenyl]-2,2-difluoro-2 H-2λ4,3λ4-benzo[ e][1,3,2]oxazaborinine ( TCH) at 488 nm redshifted to 571 nm upon grinding, and the ground powder exhibited an orange emission. Fuming with dichloromethane (DCM) or heating at 200 °C for 2 min led to the recovery of the original solid state that emitted a bluish-green light. XRD patterns illustrate that the mechanofluorochromism features are reasonable for the transformation between the crystalline and amorphous states. [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]

Abstract: A new D–π–A type gelator based on a phenothiazine derivative, which can gel cyclohexane, hexane, and ethanol/water under ultrasound treatment, has been synthesized. Because such gelators can act as twisted intermolecular charge transfer (TICT) probes, their emission in solution can be tuned by varying the polarity of the solvents. It is notable that an unusual aggregation-induced blue shift of the emission has been detected on account of the suppression of TICT in the gel phase. [Copyright &y& Elsevier]

Abstract: To meet the need for rapid and low-cost chemical sensing of explosive, new fluorescence chemosensors based on oligophenothiazines for probing vapor-phase nitro compounds have been developed. The phenothiazine-based trimer P3 and pentamer P5 have been synthesized via Heck and Wittig reactions by convergent approach. It was found that they can detect the vapors of nitro compounds, including p-nitrotoluene ( p -NT), 2,4-dinitrotoluene (DNT), 2,4,6-trinitrotoluene (TNT) with good sensitivity and reversibility. And the sensor of P3 film gave a linear fluorescence quenching response to 7–800ppb TNT with the detection limit of 4ppb. For DNT vapor, a linear working range of the sensor was 2–24ppm with the detection limit of 40ppb. Meanwhile, the interferents, including common organic solvents, p-nitrophenol and 2,4-dinitrophenylhydrazine cannot lead to obvious fluorescence quenching, meaning that the film based on oligophenothiazines exhibited good specificity of fluorescence response to explosive. Based on the fluorescence lifetime and UV–vis absorption measurements, we suggested that the fluorescence quenching of oligophenothiazine-based films exposed to the vapors of nitro compounds was due to the formation of non-fluorescent charge-transfer complex between oligophenothiazine and nitro compounds. [ABSTRACT FROM AUTHOR]

A novel photochromic gel film was prepared through entrapping 12-phosphotungstic acid (PWA) into a kind of inorganic–organic matrix co-hydrolyzed from tetraethylorthosilicate (TEOS) and 3-aminopropyltriethoxysilane (APTES). Infrared (IR) spectra revealed that the Keggin structure characteristic of PW12O403− anions was present in the amine-functionalized silica gel skeleton and PWA interacted with R-NH3+ cations strongly. The amorphous state of the gel film was proved by X-ray diffraction (XRD) pattern. The gel film exhibited reversible photochromicity. Irradiated with ultraviolet light, the transparent film changes from colorless to blue. Then, bleaching occurs when the film is in contact with air or O2 in the dark. [Copyright &y& Elsevier]

A novel thermochromic sol–gel film has been prepared for the first time through entrapping phosphomolybdic acid into a kind of inorganic–organic matrix co-hydrolyzed from tetraethylorthosilicate and 3-aminopropyltriethoxysilane. The thus-obtained amorphous nanocomposite film was characterized by IR spectra, UV–vis absorption spectra, XRD, TG–DTA, and ESR. Results show that phosphomolybdate polyanions interact with R–NH+3 cations strongly and disperse homogeneously in the sol-gel matrix. The sol–gel film exhibits thermochromic properties. Annealed from 120 to 180°C, the transparent film changes from pale-yellow to blue. A possible charge-transfer process has been suggested to explain the thermochromism. [Copyright &y& Elsevier]

Two push-pull compounds, which are comprised of triphenylamine (TPA) (electron donor units) and functionalized β-diketones difluorboron complexes (electron acceptor units) are probed by many spectroscopies, which offers the relationship between electron acceptor and the intrinsic excited state properties of push–pull chromophores. We found that the photoluminescence (PL) intensity would enhance with the number of electron acceptor. Transient absorption (TA) data shows that intramolecular charge transfer (ICT) process really exists in the two molecules after photoexcitation and this process would be prolonged through increasing the electron-acceptor, which would be responsible for the improvement of PL property. [ABSTRACT FROM AUTHOR]

To prepare colorless polyimides (CPIs), two novel diamines, namely 6-amino-2-(2′-methyl-4′-aminobenzene)-N-phenylbenzimidazol (5a) and 6-amino-2-(2′-trifluoromethyl-4′-aminobenzene)-N-phenylbenzimidazol (5b) were synthesized, and two series of polyimides derived from them were developed. Except for the inherent asymmetric structures, the twisted moieties had been successfully incorporated in the benzimidazole dianmines through 2′- and N-substituents. The loose chain packing and hindered charge transfer (CT) interaction caused by the askew and distorted segments provided the polyimides with excellent optical transparency (80% transmittance at 400 nm, semi-alicyclic series), while the resulting films inherited the unique superheat-resistance of poly(benzimidazole imide)s (PBIIs), e.g., high glass-transition temperatures (up to 402 °C). Such outstanding optical and thermal properties expanded their application as heat-resistant colorless materials. Furthermore, the correlation between various 2′-substituents and characters of these PBII films was systematically analyzed. These data indicated that these colorless polyimides had potential application as optical and optoelectronic materials. [Display omitted] • Two novel benzimidazole dianmines containing 2′- and N-substituents (5a and 5b) were successfully synthesized. • Polyimide films with asymmetric and twisted structures were successfully synthesized. • The semi-aromatic poly(benzimidazole imide) films achieved colorlessness (T 400 = 80–81% and T g = 394–402 °C). • The effect of various 2′-substitutions on the properties of these N-phenyl-poly(benzimidazole imide)s was investigated. [ABSTRACT FROM AUTHOR]