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Fluorescence materials have attracted great attention in the last decades because of their modulable fluorescence properties and broad applications. Molecular packing is one of the most important factors that determines organic molecular piezochromic fluorescence behavior. Herein, we systematically investigated the fluorescence, vibrational, and structural properties of chrysene up to 20 GPa by using multiple experimental techniques and ab -initio calculations. We find the obvious color-changing with increasing pressure. Meanwhile, the phase transition at a pressure of about 6.6 GPa has been identified from both the frequency shifts and the changes in intensity of the Raman modes. However, the structure of chrysene at ambient pressure remains stable to at least P∼20.2 GPa from both experimental and theoretical x-ray diffraction results. Further structural analysis indicates that the angle between two molecular planes decreases with pressure, resulting in the packing alteration. The combined results from the experiments and computations demonstrated that the observed phase transition at 6.6 GPa is probably a result of the change of molecular packing. Furthermore, the intermolecular interactions have changed correspondingly due to the change of the molecular packing, which results in the color-changing of chrysene under pressure. These results provide further evidence that the intermolecular interactions play the important role in tuning the photo-physical properties, and this work will contribute to understanding the relationship between molecular packing and piezochromism in fluorescence materials. • The crystal optical color of chrysene undergoes obvious color-changing with increasing pressure. • The mode of molecular packing of chrysene has changed under pressure. • Piezochromic luminescence behavior of chrysene is result from the changes of intermolecular interactions. [ABSTRACT FROM AUTHOR]

Flexible crystals with plasticity and elasticity that exhibit phosphorescent emission are quite rare yet highly significant for their potential applications. In our study, we present an example of such flexible (both elastic and plastic) organic crystals based on 1,2-bis(3-bromophenyl)-ethane-1,2-dione (BBPED), which demonstrates a lifetime of 0.504 ms (517 nm) and a quantum efficiency of 26.12 % at room temperature. These crystals exhibit reversible elastic properties in both their original and twisted states, and possess optical waveguide properties with minimal optical loss coefficients in the range of 0.26–0.48 dB/mm. In addition, the above crystals exhibit phosphorescence to phosphorescence blueshift under hydrostatic pressure, whereas mechanical grinding produces a phosphorescence to phosphorescence redshift phenomenon. Theoretical calculations indicate that the alterations in molecular conformation and intermolecular interactions both contribute to the piezochromic phenomenon. In conclusion, this work provides a new approach to the design of multifunctional phosphorescent molecular crystals with flexible characteristics. • Flexible crystals with plasticity and elasticity. • Crystals with 1D to 3 D phosphorescent waveguide properties. • Crystals with piezochromism properties. [ABSTRACT FROM AUTHOR]

Abstract The iso -cis/trans-aminobenzopyranoxanthenes (iso -cis/trans-ABPXs), as one of popular leuco dyes, were investigated in solution or crystal phase. The introduction of benzo-pentacyclic-ester group in iso -cis/trans-ABPXs leads to remarkable multi-stimuli responsive behaviors, including protonation effect, photochromism and piezochromism with notable color changes. The iso -cis/trans-ABPXs show different in the responsive sensitivity and the iso -cis-ABPX is highly sensitive to environmental stimuli relative to the trans-form, which can be explained by their different C-H⋯O interaction and/or C-O bond length. Interestingly, as the ultraviolet light irradiation time increasing, the iso -cis/trans-ABPXs solution gradually becomes transparent and orange precipitates are achieved, which is identified as iso -ABPXs±. Multi-stimuli responsive behaviors on the iso -cis/trans-ABPXs provide a comprehensive insight into the chromogenic mechanisms of this type of materials, suggesting that they may be potential candidate materials for sensors and indicators. Graphical abstract Image 1 Highlights • The iso -cis/trans-ABPXs show remarkable color and spectral changes under different stimuli respectively. • The iso -cis -ABPXs is more sensitive to the stimuli due to the differences in structures. • The orange solid of iso -cis/trans-ABPXs± can be produced from iso -cis/trans-ABPXs solution under the UV light irradiation. [ABSTRACT FROM AUTHOR]

Abstract Piezochromic luminescence behaviours of 9, 10-distyrylanthracene (DSA) derivatives with different substituents based on their single crystal structures were investigated under hydrostatic pressure via a diamond anvil cell (DAC), compared with the anisotropic force produced from grinding. Upon grinding, three single crystals show identifiable blue-shifts in fluorescent spectra because of the disturbance for ordered crystal structure to amorphous state, but nearly sightless color changes. The high-pressure fluorescent experiments applied by DAC reveal three DSA crystals all show large red-shifts. High pressure absorption spectra display that a new charge transfer state appears when -CH 3 or -2CN is introduced to DSA and all of them show obvious red-shifts. Once the pressure was relieved gradually to the ambient pressure, the fluorescence and absorption spectra both entirely recovered, indicating this geometric change is reversible in a certain pressure region, which is further confirmed by Raman spectra. The relationships between molecular structures and spectroscopic behaviours were further discussed by their single crystal data. This work provides deep insights into the relationship between molecular structure and photo-physical properties of practical mechanochromic luminescent materials, and is significant in the potential applications of pressure transducers. Graphical abstract Image 1 Highlights • Photo-physical behaviors of three DSA crystals with different substituents are disclosed. • DSA crystals exhibit different responses to anisotropic/isotropic pressures. • Self-recovery of DSA crystals during compression. • Remarkably large Red-shift of emission band under pressure is observed. • Introduction of -CH 3 and –CN to DSA cause a new CT state. [ABSTRACT FROM AUTHOR]

Abstract A naphthaldehyde based Schiff base, HMP has been synthesized by simple one-pot synthesis and characterized by IR, NMR and mass spectral techniques. HMP was non-emissive in acetonitrile, but its emission intensity was enhanced drastically (68 folds) upon addition of water, demonstrating typical aggregation induced emission (AIE) behaviour. Fluorescence quantum yield was increased drastically on aggregation from 0.3% (f w = 0%) to 8.1% (f w = 99%). Lifetime decay measurements were also performed in support of AIE property. Single crystal X-ray diffraction and DFT studies reveal that conformational transformation from benzenoid to quinonoid form induces restricted intramoleclar rotation (RIR) which contributes to AIE property. HMP was found to exhibit strong luminescence and piezochromism in solid state. Interestingly, dark yellow luminescence of crystalline HMP was changed to light green in response to grinding and a blue shift from 544 nm to 531 nm was observed. HMP exhibits good parent crystalline maintenance capability during grinding. Synthetic ease and reversible transformation of HMP are the key features to establish its application in pressjet printing and pressure sensing. Graphical abstract A Schiff base (E)-1-(3-(((2-hydroxynaphthalen-1-yl)methylene)amino) phenyl) displaying remarkable aggregation induced emission and unique piezochromism has been synthesized and characterized. Image 1 Highlights • A simple and cost effective Schiff base has been synthesized and characterized. • It offers a unique aggregation induced emission (AIE) and piezochromic behaviour. • UV−Vis, fluorescence spectroscopy and SEM-TEM is used to study the AIE property. • Piezochromic property is monitored by PXRD and solid state fluorescence. • It is utilised in stress detection and security technologies. [ABSTRACT FROM AUTHOR]

A series of carbazole-based diphenyl maleimide dyes with different N-substituent were synthesized through an Ullmann reaction in high yields. The dyes exhibit an intense emission in the solid state for their twisted conformation fixed by weak intermolecular interactions, resulting in the hindrance of the internal rotations. Their solid-stated emission wavelength and intensity are sensitive to external stimuli (like heat, pressure and vapor), due to a crystal-to-crystal or crystal-to-amorphous phase transition. Based on the multi-stimuli-responsive fluorescence properties of the N -benzyl analogue, two kinds of applications were explored. One is rewritable data recording processes including solvent writing and vapor writing. The other is sensing for low hydrostatic pressure (0–25 MPa). Interestingly, nanoparticles of the dyes formed in aqueous solution could effectively detect explosive and pH changes. A 15 ppm concentration of picric acid quenched the fluorescence of the N -methyl analogue with the detectable limit calculated to be 0.13 ppm. The N -methyl analogue also showed a different emission color and intensity over the pH range 12–14, which originated from the hydrolysis of the dye molecules in the strongly basic solution. [ABSTRACT FROM AUTHOR]

Three D-π-A 1,4-dihydropyridine derivatives with aggregation-induced emission characteristics were synthesized. The molecules comprise of a 4-(dimethylamino)styryl group as the electron donor group and different end groups, dicyanomethylene, vinylcyanoacetate, and 2-methylene-1 H -indene-1,3(2 H )-dione, as the electron acceptor, respectively. These target compounds display different stimulus-responsive fluorescent properties in the solid state. The original samples with the dicyanomethylene and vinylcyanoacetate groups do not show fluorescence color changes in response to external force stimuli, whereas the compound containing the 2-methylene-1 H -indene-1,3(2 H )-dione unit exhibits reversible piezochromism and solvent-induced emission changes due to the transformation between the crystalline and amorphous states, which can be ascribed to their different molecular stacking mode in the solid state. Furthermore, these compounds show different acid/base-induced solid-state fluorescence switching properties due to the different sites of the protonation. Additionally, all of the derivatives can be fabricated into biocompatible fluorescent nanoparticles and used for MCF-7 cell imaging. [ABSTRACT FROM AUTHOR]

A close-bonded D-A-D′ luminophore BOTPA was designed via direct coupling of secondary arylamine derivatives (D, D′) with benzothiadiazole cyanostilbene group (A). Both near-infrared (NIR) aggregation-induced emission (AIE) and hybridized local and charge-transfer (HLCT) effects, which endow it with highly efficient NIR piezochromic performance, are observed owing to its especially short D-A distance and twisted conformation. The luminophore shows bright fluorescence at 740 nm with an absolute photoluminescence quantum yield (PLQY) as large as 13.2%. Remarkable piezochromism with high sensitivity (11.0 nm•Gpa−1) completely in the NIR region (700–840 nm) could be observed from BOTPA crystals, which is rarely found in piezochromic materials (PCMs). The effects of the shortened D-A distance towards the highly efficient NIR piezochromism are confirmed via single-crystal analysis, in-situ FTIR and theoretical calculations. This work provides a new strategy for the development of high-efficiency NIR PCMs which possess strong penetrating capacity. [Display omitted] • A benzothiadiazole cyanostilbene derivative BOTPA with both AIE and HLCT characters was successfully synthesized. • BOTPA crystal exhibits highly efficient near-infrared emission at 740 nm with a PLQY as high as 13.2%. • Highly sensitive piezochromic property completely in the near-infrared region (700–840 nm) is performed by BOTPA. • Highly twisted conformation endows BOTPA with such a strong pressure resistance that can still emit under 12 GPa. [ABSTRACT FROM AUTHOR]

Abstract: In this work, a series of luminogens comprised of tetraphenylethene plus spirobifluorene or 9,9-diphenylfluorene are synthesized and characterized. Whereas these luminogens are weakly fluorescent in solutions, they are highly emissive in the aggregated state, with high fluorescence quantum yields up to 99% in solid films, demonstrating aggregation-induced emission characteristics. Reversible piezochromic luminescence is observed from the solids of the luminogens. A notable emission color change from blue (445 nm) to green (503 nm) is readily realized by grinding the pristine powder of the luminogen. The blue emission is recovered by fuming the ground powder with dichloromethane vapor. The undoped electroluminescence devices using the luminogens as light-emitting layers are fabricated, affording high current efficiencies up to 7.2 cd/A. [Copyright &y& Elsevier]

Eleven (E)-4-t-butyl-1-(4-dimethylaminobenzylideneamino)pyridinium perchlorates were obtained by the condensation of 1-amino-4-t-butylpyridinium perchlorate with p-amino-benzaldehydes. The position of the primary band in their UV/VIS spectra was not simply related to the σ substituent constants of the different amino groups. Only two compounds were found to be fluorescent and piezochromic. [Copyright &y& Elsevier]

Two polymorphs of 9,10-bis(phenylethynyl)anthracene (OC and RC) were obtained and they were characterized by multi spectroscopies including X-ray diffraction, absorption, fluorescence and Raman. The single-crystal structure analysis shows that RC has richer intermolecular interactions (C–H ... π and C–H⋯H–C) than OC, which accounts for different spectroscopic behaviors of RC from OC in high pressure studies. Under mechanical grinding, two polymorphs have similar spectral changes in their fluorescence as significant enhancement and slight blue-shifts of the shoulder emission bands at lower wavelength, except that RC shows more sensitive to grinding than OC. During the compression process applied by diamond anvil cell (DAC), OC and RC both demonstrate remarkable red-shifts with increasing pressure, while RC shows a smaller shifting rate than OC. These spectral phenomena reveal that the richer intermolecular interactions in RC can be easily destroyed upon grinding. This work provides the in-depth insight into the mechanism of mechanochromism and the structure-property relation, and proves again that the intermolecular interactions play the key role in modulating the photo-physical properties. Image 1 • Pressure induced enhancement of the shoulder emission intensity at lower wavelength of two polymorphs upon grinding. • OC and RC show different responses to pressure. • Intermolecular interactions answer for different photo-physical properties of two polymorphs. [ABSTRACT FROM AUTHOR]