Yujian Zhang

Multicolored-Fluorescence Switching of ICT-Type Organic Solids with Clear Color Difference: Mechanically Controlled Excited State

A donor-acceptor-type fluorophore containing a twisted diphenylacrylonitrile and triphenylamine has been developed by using the Suzuki reaction. The system indicates typical intramolecular charge-transfer properties. Upon mechanical grinding or hydrostatic pressure, the fluorophore reveals a multicolored fluorescence switching. Interestingly, a fluorescence color transition from green to red was clearly observed, and the change of photoluminescent (PL) wavelength gets close to 111 nm. The mechanisms of high-contrast mechanochromic behavior are fully investigated by techniques including powder XRD, PL lifetime, high-pressure PL lifetime, and Raman spectra analysis. The tremendous PL wavelength shift is attributed to gradual transition of excited states from the local excited state to the charge-transfer state.

A donor–acceptor cruciform π-system: high contrast mechanochromic properties and multicolour electrochromic behavior

A donor–acceptor (D–A) cruciform conjugated luminophore DMCS-TPA was designed and synthesized. The DMCS-TPA solid shows both aggregation induced emission (AIE) effect and high contrast mechanochromic (MC) behavior with a remarkable spectral shift of 87 nm. The obvious fluorescence switching from yellowish green to orange can be realized by pressing at only 10 MPa or simply grinding. The photophysical properties, theory calculation and XPS results demonstrate that the extension of the conjugation length and subsequent enhancement of intramolecular charge transfer (ICT) transition are responsible for the improved MC performance. In addition, DMCS-TPA is readily deposited on the ITO electrode surface by the electrochemical method to form an electrochromic (EC) film with multiple colours showing (light green at 0 V, red at 1 V, grey at 1.1 V and blue at 1.45 V) and a high optical contrast of 65% at 769 nm. The results suggest that incorporation of electroactive moieties into luminophores to constitute D–A cruciform conjugated structures is a promising design strategy for preparing dual functional materials combining MC and EC properties.

Heating and mechanical force-induced luminescence on–off switching of arylamine derivatives with highly distorted structures

A triphenylamine-based organic luminophor (TPA-CO) with a highly distorted structure has been designed and effortlessly obtained by an Ullmann reaction. The luminophor exhibits a stimuli-induced emission enhancement effect and intramolecular charge transfer properties. The fluorescence efficiency of its crystals is dramatically increased from 0.4% to 12.3% upon grinding. The emission enhancement is also realized by a heating process. The “bright” state can recover its original state and turn “dark”. The luminescence “on–off” behaviour is repeatedly transformed by a grinding–vapour process or by a heating process. The XRD patterns of the “bright” and “dark” states show that the change of emission intensity is related to the reversible transition between the crystalline state and the metastable amorphous state. At the molecular level, the emission enhancement upon external stimuli may be attributed to conformational planarization and weak intermolecular interactions.

Polymorphic crystals and their luminescence switching of triphenylacrylonitrile derivatives upon solvent vapour, mechanical, and thermal stimuli

For piezo-, vapo-, and thermochromic materials, it remains a challenge to figure out the underlying reason for fluorescence color changes upon external stimulation and determine why only some fluorophores reveal emission switching. A novel triphenylacrylonitrile derivative (TPAN-MeO) with remarkably twisted conformations has been carefully prepared via the Suzuki coupling reaction. The fluorescence of TPAN-MeO in the aggregate state depends on the polymorphic forms: three crystalline forms BCrys, SCrys and YCrys exhibit bright blue, sky-blue and yellow emission, respectively; meanwhile the amorphous powders are also strongly fluorescent with green emission. The crystals BCrys and SCrys exhibit mechano- and piezochromism in that grinding and high pressure could alter the emission colour, respectively. In addition, the amorphous film exhibits vapo- and thermochromic behaviour in that organic vapour and heating could change the green colour into sky-blue. Interestingly, the solvent vapour and heating stimuli can trigger a crystal-to-crystal transformation between SCrys form and YCrys form.

Unique torsional cruciform π-architectures composed of donor and acceptor axes exhibiting mechanochromic and electrochromic properties

A series of unprecedented bifunctional materials response to both mechanical and electrical stimuli have been developed with torsional cruciform π-architectures composed of donor and acceptor axes. These cross-conjugated geometries possess spatially separated HOMO and LUMO located on the donor and acceptor axis, respectively. A unique charge transfer (CT) process from one axis to the other in the excited state is evidenced by theoretical calculations and spectral analysis. This unusual electronic nature along with the conformational flexibility of compounds is found to be significant for their effective mechanochromic (MC) and electrochromic (EC) performances. Through changing substituents on one bar, systematic and comparative studies have been carried out to explore the structural impacts on the MC and EC properties. Based on the structure–property relationships, remarkable MC materials with emission shifts above 70 nm and excellent EC materials with high optical contrast (70%) and fast response time (0.59 s for fading, 1.44 s for colouring) are obtained. Besides, an effective method for selectively modulating the LUMO energy level as well as bandgap is also attained.

Polymeric electrochromic materials with donor–acceptor structures

Conjugated polymers with various electron-donor (D) and -acceptor (A) structures have been an important focus in the field of electrochromic (EC) research. Recent years have witnessed significant advances in the context of the design and synthesis of D–A type conjugated polymers. Most studies have investigated tunable band gap and color changes by introducing appropriate D and A units. However, D–A polymers with specific D units containing A units in the backbone or side chain possess varied ionization potentials, electron affinities and conjugation effects, leading to diverse electrochemical, optical-physical and EC properties. In addition, some innovative D–A structural polymers, such as cruciform and dendritic structures, present superior EC properties as well as multifunctional performance. In this review, our main focus will be placed on summarizing the characteristics of polymeric EC materials with various donor–acceptor structures. The overarching aim is to strengthen the understanding of the relationship between the D–A structure and the EC properties, especially color characteristics, and to provide some suggestions for the design of novel multifunctional D–A polymers for the future.

Fluorescence mutation and structural evolution of a π-conjugated molecular crystal during phase transition

Two thermodynamically stable crystalline phases (B- and G-phases) were found for a twistable π-conjugated molecule, CN-DSB, condensed from its solution. We investigated the structural evolution at the molecular and supramolecular levels as the crystalline phase transforms from the B-phase to G-phase under varied temperature or pressure. The intermolecular interactions were undermined before phase transition as the B-phase crystal was stimulated with an external energy. Heating the B-phase crystal up to 175 °C or applying stress up to its critical pressure (0.75 GPa) initially resulted in mixture phases or disordered state. At this stage, the molecules slightly adjust from a twisting configuration to a planar configuration, corresponding to the gradual red shift of the fluorescence spectra. Above the phase transition point, the initial intermolecular interaction of the B-phase is broken down, and the CN-DSB molecules re-assemble to the new phase—a new thermodynamic equilibrium state—corresponding to the sudden change of the emission color. Furthermore, the property of thermal-induced phase transition can be used to fabricate patterns on the CN-DSB crystal surface, and a uniform raster has been prepared by femtosecond laser direct writing (FsLDW) on the B-phase. The investigations provide new insight and understanding for the crystal phase transition and may contribute to process innovation in optical devices.

Heating and mechanical force-induced “turn on” fluorescence of cyanostilbene derivative with H-type stacking

A cyanostilbene-based derivative with aggregation induced-emission was obtained, which exhibited multi-luminescent intensity under external stimuli. The as-prepared crystals of the desired dye showed a rather faint luminescence. Upon heating, its fluorescence could be turned on with the quantum yields of 13.3%. The quantum yields of the melted and solidified powders were further increased to 28.6%. Powder X-ray diffractometry, fluorescence spectroscopy, fluorescence lifetime experiments and single crystal XRD analyses were applied to investigate the changes of molecular packing modes. Such a transformation of fluorescence “dark”–“bright”, easily distinguished by naked eye, was related to the phase transition. The planar cyanostilbene with H-type packing and multiple mutable interactions may be the essential factor for the multi-luminescent intensity properties.

Effect of stacking mode on the mechanofluorochromic properties of 3-aryl-2-cyano acrylamide derivatives

Three structurally simple 3-aryl-2-cyano acrylamide derivatives, 2-cyano-3-(2-methoxyphenyl)-2-propenamide (1), 2-cyano-3-(3-methoxyphenyl)-2-propenamide (2) and 2-cyano-3-(4-methoxyphenyl)-2-propenamide (3) were synthesized. They exhibited different optical properties due to their distinct face-to-face stacking mode. The as-prepared crystals of 1 exhibited green luminescence and the emission peak did not change after grinding treatment. However, the emission peaks of 2 (Φf = 12%) and 3 (Φf = 16%) exhibited an obvious red-shift upon grinding, and their corresponding quantum yields decreased to 8% and 10%, respectively. Differential scanning calorimetry and powder X-ray diffractometry data indicated that the optical properties of 2 and 3 could be attributed to the transformation from the crystalline phase to the amorphous phase. X-ray crystal structures, infrared spectroscopy and data from fluorescence lifetime experiments further validated the relationship between fluorescence switching, stacking mode and molecular interactions.

Clear piezochromic behaviors of AIE-active organic powders under hydrostatic pressure

A novel diphenylacrylonitrile derivative (Z)-3-(4′-(diphenylamino)-[1,1′-biphenyl]-4-yl)-2-(4-methoxyphenyl)-acrylonitrile (β-CN-TPA) containing a twisted triphenylamine and diphenylacetonitrile was synthesized via Knoevenagel condensation and Suzuki coupling reactions. These molecules exhibited aggregation enhanced emission (AIE) effects. Interestingly, their mechano-fluorochromic properties were invisible upon grinding with a pestle. However, when hydrostatic pressure in a diamond anvil cell (DAC) was applied on the crystals of β-CN-TPA, the distinct piezochromic behaviors of the compound were observed. The fluorescence color changed from light green (530 nm) to red (665 nm) with a significant red-shift of 135 nm. The powder X-ray diffraction and high-pressure Raman studies indicated that the as-synthesized and ground samples had the same crystalline structures, while the compressed samples had an evident change in inter-molecular interactions. Comparative tests and theoretical analysis further confirmed that the distinct fluorescence behaviors of the desired dye during the different stress conditions were associated with the various inter-molecular interactions that existed with adjacent molecules.