Xiaojing Lv

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.

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.

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.

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.

A core–shell composite of porous ZnO nanosheets and a multichromic conducting polymer: enhanced electrochromic performances

A core–shell composite of porous ZnO nanosheets and a multichromic conducting polymer poly(4,4′,4′′-tris[4-(2-bithienyl)pheny]amine) (PTBTPA) was prepared by electrodeposition combined with the electropolymerization method. The composite film exhibits noticeable electrochromism with reversible color changes from orange, olive green to dark gray. An optical contrast of 68.7% and a switching time of 0.96 s are obtained for the composite film, better than that of the pure PTBTPA film, 51.8% and 1.95 s. The cyclic stability studies reveal that the composite film exhibits much more enhanced durability and retains 70% of the electroactivity even after 1000 cycles. However, the pure PTBTPA film loses almost most of its electroactivity after 1000 cycles. The core–shell composite structure is believed to be responsible for the observed enhanced electrochromic performance. On one hand, porous ZnO nanosheets with loose inner space can facilitate the penetration of counterions into the polymer film and shorten the diffusion distance, resulting in the higher optical contrast and faster switching speed; on the other hand, the larger contact area can enhance the adhesion between the polymer and the ITO electrode, contributing to better electrochemical stability.

Enhanced electrochromic switching speed and electrochemical stability of conducting polymer film on an ionic liquid functionalized ITO electrode

The 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM]BF4) functionalized ITO substrate was successfully prepared via a solution immersion method and then incorporated with poly(4,4′,4′′-tris[4-(2-bithienyl)phenyl]amine) (PTBTPA) to form the PTBTPA–[BMIM]BF4 film by electrochemical polymerization, which presents reversible multicolor changes from orange, olive green to dark gray. Interestingly, compared with the bleaching time (tb) and the coloring time (tc) of the pure PTBTPA film (1.76 s and 4.51 s) at 1100 nm, the PTBTPA–[BMIM]BF4 film exhibits shorter tb and tc (0.87 s and 2.90 s) at the same wavelength. Obviously, the switching speed of the PTBTPA–[BMIM]BF4 film has been improved significantly, and it is further supported by the electrochemical impedance spectra which demonstrate that the PTBTPA–[BMIM]BF4 film possesses much lower charge transfer resistance. The reduction of charge transfer resistance could be attributed to (1) the private channel provided by the ionic liquid [BMIM]BF4 as a linker between the polymer and the electrode; (2) the ability of the simultaneous doping and dedoping of ClO4− in the electrolyte and BF4− ions of the ionic liquid. Moreover, the cyclic stability studies reveal that the PTBTPA–[BMIM]BF4 film exhibits better durability and retains 70.4% of its original electroactivity after 500 cycles in ionic liquid solution. The results demonstrate that the electrochemical and the electrochromic performances could be significantly enhanced through incorporating PTBTPA with the ionic liquid ([BMIM]BF4).

A fast electrochromic polymer based on TEMPO substituted polytriphenylamine.

A novel strategy to obtain rapid electrochromic switching response by introducing 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) moiety into polytriphenylamine backbone has been developed. The electrochromic properties of the integrated polymer film are investigated and a possible mechanism is proposed with TEMPO as a counterion-reservoir group to rapidly balance the charges during electrochromic switching, which leads to significantly improved electrochromism performance.

The Effect of Substituent Position on Excited State Intramolecular Proton Transfer in Benzoxazinone Derivatives: Experiment and DFT Calculation

The preparation and the photophysical behaviour of two benzoxazinone derivatives isomers 2-(1-hydroxynaphthalen-2-yl)-4H-benzo[e][1, 3]oxazin-4-one(1) and 2-(3-hydroxynaphthalen-2-yl)-4H-benzo[e][1, 3]oxazin-4-one(2) designed for displaying were reported. The effect of substituent position and solvent effect on the excited state intramolecular proton transfer (ESIPT) dynamics and the spectroscopic properties were investigated using a combined theoretical (i.e., time-dependent density function theory (DFT)) and experimental (i.e., steady-state absorption and emission spectra and time-resolved fluorescence spectra) study. The results showed that compound 1 would facilitate ESIPT process and favored the keto tautomer emission, while compound 2 suppressed the ESIPT process and favored the enol emission.

Fabrication of Nano/Microstructure of Cyano Substituted Oligo(para-phenylenevinylene) with Aggregation-Induced Emission and Morphology Dependent Luminescence

A new cyanostilbene based molecule, (2Z,2′Z)-3,3′-(4,4′′-dimethyl-[1,1’:4′,1′′-terp-henyl]-2′,5′-diyl)bis(2-(3-methoxyphenyl)acrylonitrile) (DMCS-PMP), has been designed and synthesized. Photoluminescence spectrum (PL) and scanning electron microscopy (SEM) analyses indicated that DMCS-PMP possessed extraordinary aggregation-induced emission behavior as well as morphology dependent luminescence property. Moreover, multiple intriguing nano/microstructures, including hollow sphere, spindle-like net and belt, have been fabricated via a simple reprecipitation method by varying the solvent, concentration and aging time. The hollow spheres and porous spindle-like networks are promising candidates for construction of functional optoelectronic devices, catalysts and sensors.

Self-Assembly of Cyanostilben-Based Intramolecular Charge-Transfer Compounds

A handful of cyano-stilbene derivatives are successfully synthesized through Williamson and Suzuki reaction. The dipole-dipole interaction of intramolecular charge-transfer molecule is used to self-assembly microstructure of the as-prepared materials. The CNS-1 microstructures are large-scale spherical particles. However, compound CNS-2 forms straight one-dimensional (1-D) microribbons. Additionally, the morphology of micro-structures obtained from compounds CNS-3 and CNS-5 are large-scale spheres with several micrometres.