Exploiting Mixed Valence Charge Transfer for Electrochromic and Electrofluorochromic Use.

An asymmetric mixed valence fluorophore with two different electron rich termini was investigated as a dual-role active material for electrochromism and electrofluorochromism. The fluorescence quantum yield (Φfl) and emission wavelength of the fluorophore were dependent on solvent polarity. The quantum yield of the material in an electrolyte gel, on a glass substrate and in a device was 40 %, 20 % and 13 % respectively. The fluorophore further underwent two near-simultaneous electrochemical oxidations. The first oxidation resulted in a 1000 nm red shift in the absorption to broadly absorb in the NIR, corresponding to the intervalence charge transfer (IVCT). Whereas the second oxidation led to a perceived green color at 715 nm with the extinction of the NIR absorbing IVCT. Owing to the dissymmetry of the fluorophore along with its two unique oxidation sites, the IVCT gives rise to a mixed valence transfer charge (MVCT). The coloration efficiency of the fluorophore in both solution and a device was 1433 and 200 cm2 C-1, respectively. The fluorescence intensity could be reversibly modulated electrochemically. The photoemission intensity of the fluorophore was modulated with applied potential in an operating electrochromic/electrofluorochromic device. Both the dual electrochromic and the electrofluorochromic behavior of the fluorophore were demonstrated.

Electrofluorochromic Switching of Heat-Induced Cross-Linkable Multi-Styryl-Terminated Triphenylamine and Tetraphenylethylene Derivatives.

High-performance electrochromic (EC) and electrofluorochromic (EFC) materials have garnered considerable interest due to their diverse applications in smart windows, optoelectronics, optical displays, military camouflage, etc. While many different EC and EFC polymers have been reported, their preparation often requires multiple steps, and their polymer molecular weights are subjected to batch variation. In this work, we prepared two triphenylamine (TPA)-based and two tetraphenylethylene (TPE)-based derivatives functionalized with terminal styryl groups via direct Suzuki coupling with (4-vinylphenyl)boronic acid and vinylboronic acid pinacol ester. The two novel TPE derivatives exhibited green-yellow aggregation-induced emission (AIE). The EC and EFC properties of pre- and post-thermally treated derivatives spin-coated onto ITO-glass substrates were studied. While all four derivatives showed modest absorption changes with applied voltages up to +2.4 V, retaining a high degree of optical transparency, they exhibited obvious EFC properties with the quenching of blue to yellow fluorescence with IOFF/ON contrast ratios of up to 7.0. The findings therefore demonstrate an elegant approach to preparing optically transparent, heat-induced, cross-linkable styryl-functionalized EFC systems.

A Piezoelectric-Driven Electrochromic/Electrofluorochromic Dual-Modal Display Device.

Electrochromic (EC) reflective displays offer great advantages in delivering information and providing visual data, but are limited in dark environments. Reflective/emissive dual-modal displays capable of electrochemically-induced color and fluorescence change simultaneously are highly desirable, especially possessing rapid response speed as well as long-term durability. Herein, an electroactive fluorescent ionic liquid based on triphenylamine and imidazole (EFIL-TPA) has been synthesized for reflective/emissive dual-modal display. The resultant device exhibits outstanding electrochromic/electrofluorochromic (EC/EFC) performance with low driving voltage (below 1.0 V), fast switching speed (0.57-1.8 s), and remarkable cycling durability (91% retention for 10 000 cycles). A piezoelectric nanogenerator (PENG) driven EC/EFC integrated system is fabricated to harvest energy from human motion and visually drive the color/fluorescence change for human motion indication in both bright and dark environments. This innovative EC/EFC dual-modal display device based on EFIL-TPA supports a huge space for the development of self-powered human motion visualized indication in all-light conditions.

Survey of Recent Advances in Molecular Fluorophores, Unconjugated Polymers, and Emerging Functional Materials Designed for Electrofluorochromic Use.

In this review, recent advances that exploit the intrinsic emission of organic materials for reversibly modulating their intensity with applied potential are surveyed. Key design strategies that have been adopted during the past five years for developing such electrofluorochromic materials are presented, focusing on molecular fluorophores that are coupled with redox-active moieties, intrinsically electroactive molecular fluorophores, and unconjugated emissive organic polymers. The structural effects, main challenges, and strides toward addressing the limitations of emerging fluorescent materials that are electrochemically responsive are surveyed, along with how these can be adapted for their use in electrofluorochromic devices.

Panchromatic Fluorescence Emission from Thienosquaraines Dyes: White Light Electrofluorochromic Devices.

Electrofluorochromic devices (EFCDs) that allow the modulation of the light emitted by electroactive fluorophores are very attractive in the research field of optoelectronics. Here, the electrofluorochromic behaviour of a series of squaraine dyes was studied for the first time. In solutions, all compounds are photoluminescent with maxima located in the range 665-690 nm, characterized by quantum yields ranging from 30% to 4.1%. Squaraines were incorporated in a polymer gel used as an active layer in all-in-one gel switchable EFCDs. An aggregation induced quenching occurs in the gel phase, causing a significant decrease in the emission quantum yield in the device. However, the squaraines containing the thieno groups (thienosquaraines, TSQs) show a panchromatic emission and their electrofluorochromism allows the tuning of the fluorescence intensity from 500 nm to the near infrared. Indeed, the application of a potential difference to the device induces a reversible quenching of their emission that is significantly higher and occurs at shorter switching times for TSQs-based devices compared to the reference squaraine dye (DIBSQ). Interestingly, the TSQs fluorescence spectral profile becomes more structured under voltage, and this could be explained by the shift of the aggregates/monomer equilibrium toward the monomeric species, due to electrochemical oxidation, which causes the disassembling of aggregates. This effect may be used to modulate the colour of the fluorescence light emitted by a device and paves the way for conceiving new electrofluorochromic materials based on this mechanism.

Electrofluorochromic detection of cyanide anions using a nanoporous polymer electrode and the detection mechanism.

An electrofluorochromic (EFC) conjugated copolymer (PEFC) containing carbazole and benzothiadiazole (BTD) moieties is synthesized through Suzuki coupling followed by electrochemical polymerization, resulting in a nanoporous EFC polymer electrode. The electrode exhibits high sensitivity and selectivity in the EFC detection of cyanide anions (CN(-)) in largely aqueous electrolyte (67 vol % water) because electrochemical oxidation of PEFC leads to significant fluorescence quenching, and the presence of different concentrations (1 to 100 µM) of CN(-) in the electrolyte can weaken the oxidative quenching to substantially different extents. Although PEFC is hydrophobic in the neutral state, it is converted to radical cation/dication states upon oxidation, rendering the PEFC some hydrophilicity. Moreover, its nanoporous morphology provides a large surface area and short diffusion distance, facilitating the movement of CN(-) in the electrolyte into the PEFC film to interact with receptors. Density functional theory calculations show that the noncovalent interaction between electron-deficient BTD and nucleophilic CN(-) is energy favorable in the oxidized states in both aqueous and organic media, suggesting that the specific π(-)-π(+) interaction plays the main role in the CN(-) detection.

Biomimetic Exploration and Reflection on Switchable Coordination and Narrow-Band Electrofluorochromic Devices.

Electrofluorochromic (EFC) materials and devices with controllable fluorescence properties show great application potential in advanced anticounterfeiting, information storage and display. However, the low color purity caused by the broad emission spectra and underperforming switching time of the existing EFC materials limit their application. Through biomimetic exploration and the study of reversible electrochemical responsive coordination reactions, boron-nitrogen embedded polyaromatics (B,N-PAHs) with narrow-band emission and high color purity have been successfully integrated into EFC systems, which also help to better understand the role of boron in biological activity. The EFC device achieve good performance containing quenching efficiency greater than 90% within short switching time (ton: 0.6 s, toff: 2.4 s), and nearly no performance change after 200 cycles test. Three primary color (red, green, and blue) EFC devices are successfully prepared. In addition, new phenomena are obtained and discussed in this biomimetic exploration of related boron reactions. The success and harvest of this exploration are expected to provide new ideas for optimizing properties and broadening applications of EFC materials. Moreover, it may provide ideas and reference significance for further exploring and understanding the function of boron compounds in biological systems.

Dual-Switching Electrochromism and Electrofluorochromism Derived from Diphenylamine-Based Polyamides with Spirobifluorene/Pyrene as Bridged Fluorescence Units.

Electrochromic (EC)/electrofluorochromic (EFC) bifunctional materials are receiving great attention because of their promising applications in optoelectronic devices. However, the development of ideal EC/EFC bifunctional materials is still a great challenge because of the poor integration of EC/EFC performances (optical contrast, response speed, and switching stability). Herein, we reported two novel diphenylamine-based mixed valence (MV) polyamides (S-HPA and P-HPA) with spirobifluorene (2,7-positions) and pyrene (1,6-positions) as bridged fluorescence units, respectively, showing impressive cyclability and fluorescence contrast with rapid switching. Through the formation of an effective electronic coupling between the two nitrogen centers using spirobifluorene/pyrene bridges, we demonstrated that different bridges have significant effects on the thermal and electrooptical characteristics of polyamides. In addition to lower fluorescence quantum yield and glass transition temperature, the S-HPA exhibited superior cyclability (contrast change <3.4%/14% over 500/300 cycles for EC/EFC switching), higher color/fluorescence contrast (64%/304%), and faster switching time (<2.6 s), mainly owing to the shorter conjugated length and more twisted configuration of the spirobifluorene bridge. The design principle of MV polymers with fluorophore bridges proposed here will be a promising way to realize high-performance EC/EFC devices and will also provide new insights into their future development and applications.

Electrofluorochromic Device Based on a Redox-Active Europium(III) Complex.

Electrofluorochromism owing to redox reactions on the center europium (Eu) ion in ionic liquids is examined for the helicate complexes (abbreviated as EuL) with a hexadentate pyridine derivative. Typical electrofluorochromism requires extra electroactive units complementing intra- or intermolecular energy transfer to quench fluorophores. Herein, an unprecedentedly simplified electrofluorochromic system overcoming such issues is demonstrated by utilizing reversible electrochemistry of EuL between Eu3+ and Eu2+, which accompanies large emission transition. A three-electrode electrochemical switching device is facilely prepared with an ionic liquid [BMIM][PF6] and EuL mixture. Benefiting from the stable helical coordinated structure of the ligand in [BMIM][PF6], highly enhanced red fluorescence of EuL with small quantity (≤1 wt %) is utilized. Rapid response and large contrast of luminescence are achieved: the emission is drastically quenched at the reduced state (Eu2+) and it is successfully restored by subsequent oxidation (Eu3+). The reversible fluctuation of excitation and emission spectra of an electrofluorochromic device is achieved in the potential window within ±2 V. The device affords excellent optoelectric properties in terms of well-controlled luminescence switching depending on the applied potentials and its durability. This work paves an efficient and smart way toward Eu luminescence control in optoelectronic devices.

Electroluminochromic Materials: From Molecules to Polymers.

Electroluminochromism is an interesting property found in certain classes of molecules and polymers whose photoluminescence can be modulated through the application of an external electrical bias. Unlike electrochromic materials, electroluminochromic counterparts and their applications are comparatively fewer in quantity and are less established. Nonetheless, there prevails an increasing interest in this class of electro-active materials due to their potential applications in optoelectronics, such as smart-displays, and chemical and biological sensing. This review seeks to showcase the different classes of electroluminochromic materials with focus on (i) organic molecules, (ii) transition metal complexes, and (iii) organic polymers. The mechanisms and electroluminochromic performance of these classes of materials are summarized. This review should allow scientists to have a better and deeper understanding of materials design strategies and, more importantly, structure-property relationships and, thus, develops electroluminochromic materials with desired performance in the future.

AIE-Active Polyamide Containing Diphenylamine-TPE Moiety with Superior Electrofluorochromic Performance.

Electrofluorochromism has attracted great attention due to the intelligence optoelectronic and sensing applications. The intrinsically switchable fluorophores with high solid-state fluorescence are regarded as key for ideal electrofluorochromic materials. Here, we reported an AIE-active polyamide with diphenylamine and tetraphenylethylene units, showing high fluorescence quantum yield up to 69.1% for the solid polymer film and stable electrochemical cycling stability. The polyamide exhibited reversible color and emission switching even in hundreds of cycles, and the fluorescence on/off contrast ratio was determined up to 417, which is the highest value to our knowledge. Furthermore, as the response time is vital for the real-life applications, to speed up the response of electrofluorochromism, a porous polymer film was readily prepared through a facile method, notably exhibiting high fluorescence contrast, long-term stability and obviously improved response, due to the sharply increased surface area. Therefore, the AIE-functionalization combining the porous structure strategy will synergistically and dramatically improve the electrofluorochromic performance, which will also promote their practical applications in the near future.

Tunable electrofluorochromic device from electrochemically controlled complementary fluorescent conjugated polymer films.

The fluorescent behavior of the electrofluorochromic devices (Type I) of greenish-yellow emitting P1 and blue emitting P2 can be reversibly switched between the nonfluorescent (oxidized) state and the fluorescent (neutral) state with a superb on/off ratio of 23.8 and 21.9, respectively. Moreover, a tunable electrofluorochromic device (Type II) based on two P1 and P2 polymeric layers that are coated individually on two independent ITO electrodes shows switchable blue-white-(greenish-yellow) multifluorescence states.