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.

Spectrum Reconstruction Model Based on Multispectral Electrochromic Devices.

Reconstructing the visible spectra of real objects is critical to the spectral camouflage from emerging spectral imaging. Electrochromic materials exhibit unique superiority for this goal due to their subtractive color-mixing model and structural diversity. Herein, a simulation model is proposed and a method is developed to fabricate electrochromic devices for dynamically reproducing the visible spectrum of the natural leaf. Over 20 kinds of pH-dependent leuco dyes have been synthesized/prepared through molecular engineering and offered available spectra/bands to reconstruct the spectrum of the natural leaf. More importantly, the spectral variance between the device and leaf is optimized from an initial 98.9 to an ideal 10.3 through the simulation model, which means, the similarity increased nearly nine-fold. As a promising spectrum reconstruction approach, it will promote the development of smart photoelectric materials in adaptive camouflage, spectral display, high-end encryption, and anti-counterfeiting.

An electrochemically responsive B-O dynamic bond to switch photoluminescence of boron-nitrogen-doped polyaromatics.

Boron-doped polycyclic aromatic hydrocarbons exhibit excellent optical properties, and regulating their photophysical processes is a powerful strategy to understand the luminescence mechanism and develop new materials and applications. Herein, an electrochemically responsive B-O dynamic coordination bond is proposed, and used to regulate the photophysical processes of boron-nitrogen-doped polyaromatic hydrocarbons. The formation of the B-O coordination bond under a suitable voltage is confirmed by experiments and theoretical calculations, and B-O coordination bond can be broken back to the initial state under opposite voltage. The whole process is accompanied by reversible changes in photophysical properties. Further, electrofluorochromic devices are successfully prepared based on the above electrochemically responsive coordination bond. The success and harvest of this exploration are beneficial to understand the luminescence mechanism of boron-nitrogen-doped polyaromatic hydrocarbons, and provide ideas for design of dynamic covalent bonds and broaden material types and applications.

Sustainable, low-cost, high-contrast electrochromic displays via host-guest interactions.

Electrochromic (EC) displays with electronically regulating the transmittance of solar radiation offer the opportunity to increase the energy efficiency of the building and electronic products and improve the comfort and lifestyle of people. Despite the unique merit and vast application potential of EC technologies, long-awaited EC windows and related visual content displays have not been fully commercialized due to unsatisfactory production cost, durability, color, and complex fabrication processes. Here we develop a unique EC strategy and system based on the natural host and guest interactions to address the above issues. A completely reusable and sustainable EC device has been fabricated with potential advantages of extremely low cost, ideal user-/environment friendly property, and excellent optical modulation, which is benefited from the extracted biomass EC materials and reusable transparent electrodes involved in the system. The as-prepared EC window and nonemissive transparent display also show comprehensively excellent properties: high transmittance change (>85%), broad spectra modulation covering Ultraviolet (UV), Visible (Vis) to Infrared (IR) ranges, high durability (no attenuation under UV radiation for more than 1.5 mo), low open voltage (0.9 V), excellent reusability (>1,200 cycles) of the device's key components and reversibility (>4,000 cycles) with a large transmittance change, and pleasant multicolor. It is anticipated that unconventional exploration and design principles of dynamic host-guest interactions can provide unique insight into different energy-saving and sustainable optoelectronic applications.

"Z"-Type Tilted Quasi-One-Dimensional Assembly of Actinide-Embedded Coinage Metal Near-Plane Superatoms and Their Optical Properties.

In this work, a novel discovery that the coinage-metal near-plane superatoms (CM-NPSs) formed by embedding actinide elements into the coinage metal rings can realize the "Z"-type tilted quasi-one-dimensional (1D) direct assembly is reported. This success can be attributed to the strong bonding between the overlapping parts of adjacent superatomic motifs. First-principles calculations reveal that the motifs maintain their geometric and electronic structures robustly during the assembly process. With the accumulation of motifs, the intensity of the absorption peak increases continuously in the ultraviolet-visible (UV-Vis) absorption spectra range of 300-450 nm, resulting in the hyperchromic effect, which is closely related to the degree of the participation of Th atoms. Furthermore, the absorption spectra show a continuously tunable feature in the 450-900 nm range, as the interlayer stacking pattern leads to a pronounced redshift. More importantly, the valence 5f-shells of Th atoms have an increased contribution to the final orbitals of electronic transition, which demonstrates the advantages of the active high angular momentum electrons of actinide elements in spectral properties. These findings provide a valuable reference for the direct artificial assembly of near-plane superatoms and optical properties of superatomic assemblies embedded with rare elements.

"Enzyme-Like" Spatially Fixed Polyhydroxyl Microenvironment-Activated Hydrochromic Molecular Switching for Naked Eye Detection of ppm Level Humidity.

The detection and monitoring of ultralow humidity (<100 ppm) are critical in many important industries, such as high-tech manufacturing, scientific research, and aerospace. However, the development of ppm level humidity sensors with portability, low cost, and ease of regeneration remains a significant challenge. Herein, an innovative "enzyme-like" construction strategy is proposed to address this problem by employing suitable molecular-level humidity-sensitive units and chemically constructing a multilevel spatial synergistic sensitization microenvironment around it. The as-prepared ultralow humidity-sensitive paper (UHSP) achieved a naked eye recognition humidity of 0.01-100 ppm. UHSP not only is simple to prepare, handy and low-cost, but can also be simply and efficiently regenerated as well as recycled many times by skillfully utilizing the "unconventional sublimation" and "lime slaked" of calcium oxide. The molecular reaction mechanisms involved in the humidity response and regeneration of UHSP have been demonstrated in detail. UHSP can provide a promising new method for ultralow humidity detection in the form of portable kits or sirens. The demonstrated "enzyme-like" construction strategy can bring unlimited ideas and implications to the design and development of sensors with tunable response thresholds, particularly high sensitivity.

Emerging Electrochromic Materials and Devices for Future Displays.

With the rapid development of optoelectronic fields, electrochromic (EC) materials and devices have received remarkable attention and have shown attractive potential for use in emerging wearable and portable electronics, electronic papers/billboards, see-through displays, and other new-generation displays, due to the advantages of low power consumption, easy viewing, flexibility, stretchability, etc. Despite continuous progress in related fields, determining how to make electrochromics truly meet the requirements of mature displays (e.g., ideal overall performance) has been a long-term problem. Therefore, the commercialization of relevant high-quality products is still in its infancy. In this review, we will focus on the progress in emerging EC materials and devices for potential displays, including two mainstream EC display prototypes (segmented displays and pixel displays) and their commercial applications. Among these topics, the related materials/devices, EC performance, construction approaches, and processing techniques are comprehensively disscussed and reviewed. We also outline the current barriers with possible solutions and discuss the future of this field.

A Flexible Circularly Polarized Luminescence Switching Device Based on Proton-Coupled Electron Transfer.

Flexible circularly polarized luminescence (CPL) switching devices have been long-awaited due to their promising potential application in wearable optoelectronic devices. However, on account of the few materials and complicated design of manufacturing systems, how to fabricate a flexible electric-field-driven CPL-switching device is still a serious challenge. Herein, a flexible device with multiple optical switching properties (CPL, circular dichroism (CD), fluorescence, color) is designed and prepared efficiently based on proton-coupled electron transfer (PCET) mechanism by optimizing the chiral structure of switching molecule. More importantly, this device can maintain the switching performance even after 300 bending-unbending cycles. It has a remarkable comprehensive performance containing bistable property, low open voltage, and good cycling stability. Then, prototype devices with designed patterns have been fabricated, which opens a new application pattern of CPL-switching materials.

Multi-Component Collaborative Step-by-Step Coloring Strategy to Achieve High-Performance Light-Responsive Color-Switching.

Light-responsive color-switching materials (LCMs) are long-lasting hot fields. However, non-ideal comprehensive performance (such as color contrast and retention time cannot be combined, unsatisfactory repeatability, and non-automated coloring mode) significantly hinder their development toward high-end products. Herein, the development of LCMs that exhibit long retention time, good color contrast, repeatability, and the property of automatic coloring is reported. The realization of this goal stems from the adoption of a bio-inspired multi-component collaborative step-by-step coloring strategy. Under this strategy, a conventional one-step photochromic process is divided into a "light+heat" controlled multi-step process for the fabrication of the desired LCMs. The obtained LCMs can effectively resist the long-troubled ambient-light interference and avoid its inherent yellow background, thereby achieving the longest retention time and good repeatability. Multiple colors are generated and ultra-fast imaging compatible with the laser-printing technology is also realized. The application potential of the materials in short-term reusable identity cards, absorptive readers, billboards, and shelf labels is demonstrated. The results reported herein can potentially help in developing and designing various high-performance, switchable materials that can be used for the production of high-end products.

Dynamic Metal-Ligand Interaction of Synergistic Polymers for Bistable See-Through Electrochromic Devices.

Bistable electrochromic materials are a promising alternative solution to reduce energy consumption in displays. Limited by the mechanism and lack of a design strategy, only a few electrochromic materials have truly been able achieve bistability. Herein, a novel strategy is proposed to design bistable electrochromic materials based on polymer-assisted dynamic metal-ligand coordination. The mechanism and materials of such unconventional electrochromic systems are proved by sufficient characterization. Synergistic stabilization of polymerized switchable dyes and the ionic ligand polymer are attracted to each other by supramolecular forces. The color states of the dye molecules are controlled and stabilized by valence changes of the metal ions. Meanwhile, through the polymerization of the electrochromic material and the nearby metal-ligand material, the metal ions of the electroinduced valence change are tightly fixed, and the related diffusion problem of the active EC component is also almost completely suppressed. This strategy successfully enables preparation of the corresponding transparent electrochromic displays with good performances, such as, the display information is clearly visible for more than 1.5 h without consuming energy. Furthermore, the new way of dynamic coordination or dissociation bistable displays could likely prosper the development of the electrochromic area and inspire other fields.

Wide-Range and Highly Sensitive Chiral Sensing by Discrete 2D Chirality Transfer on Confined Surfaces of Au(I)-Thiolate Nanosheets.

Circular dichroism (CD) chiral sensing is very promising to meet the ever-increasing demands for high-throughput chiral analysis in asymmetric synthesis. However, it is still very challenging to sensitively quantify the composition of enantiomers in a wide concentration range because the existing sensing systems show either linear CD response resultant from stoichiometric chiral transfer or nonlinear CD response resultant from amplified chiral transfer and thus have the drawbacks of low sensitivity and narrow quantification range, respectively. Herein, we propose a sensing system of two-dimensional (2D) Au(I)-thiolate nanosheets. The disordered interligand interactions on the confined surfaces of nanosheets enable the formation of discrete amplified chiral domains around the adsorbed chiral analytes, resulting in a linearly amplified chiral transfer behavior, which provides a solution for highly sensitive and wide-range quantification of enantiomer compositions. Taking (1R, 2R)-(-)- and (1S, 2S)-(+)-1,2-diamino cyclohexanes as example analytes, the concentration and full-range enantiomeric excess (ee) values have been quickly determined by adsorbing them on the surface of Au(I)-MPA (MPA: 3-mercaptopropionic acid) nanosheets in the concentration range of 1.0 × 10-6 to 4.0 × 10-5 M. By engineering the surface functional groups, Au(I)-thiolate nanosheets can be extended to sense other types of analytes, and several polyols with multiple chiral centers have been sensed by boronic acid functionalized nanosheets at the 10-7 M level. The high performances, good extendibility, and one-pot high-yield aqueous synthesis ensure these Au(I)-thiolate nanosheets can be developed as a practical and powerful chiral sensing platform.

Stimuli-Induced Reversible Proton Transfer for Stimuli-Responsive Materials and Devices.

ConspectusStimuli-responsive materials have a great potential in various novel photoelectric devices, such as self-adaptive adjustment devices, intelligent detection, molecular computers with information storage capability, camouflage and anticounterfeiting display, various energy-saving displays, and others. However, progress in related areas has been relatively slow because of the lack of high-performance smart materials and the limitations of available reaction mechanisms currently. To address these problems fundamentally, new mechanisms need to be designed and developed, and learning from nature is an effective and intelligent method to achieve this long-awaited target, such as mimicking of proton transfer processes in nature at the molecular/supramolecular level. The stimuli-induced reversible proton transfer system is composed of materials that release or capture protons in response to stimuli and switch molecules that control color and/or fluorescence modulation by protons, and it is applied in stimuli-responsive materials and devices, including bistable electronic/electrochromic devices, electrofluorochromic devices, water-jet rewritable paper, visible-light-responsive rewritable paper, and mechanochromic materials.To help researchers gain deep insight into stimuli-induced reversible proton transfer, we attempted to summarize its reaction mechanism and design principle, and discuss strategies to design and prepare various related stimuli-responsive materials and devices. This Account discusses the different systems in which a color/fluorescence change is induced by the proton transfer process under various stimuli, including electric field, water, light, heat, and stress. Relative very promising applications as well as their performance especially for energy-saving and environmentally friendly devices are then summarized, such as energy-saving bistable electrochromic devices, water-jet rewritable paper, and visible-light-responsive rewritable paper. Meanwhile, we focus on the key influence factors and useful additives for improving the device's performance. At last, challenges and bottlenecks faced by stimuli-responsive materials and devices based on the mechanism of reversible proton transfer are proposed. Moreover, we put forward some suggestions on solving these limitations.These exciting results reveal that smart materials based on the mechanism of proton transfer are extremely attractive and possess great potential in the next generation of energy and resource saving and environmental protection display. We hope that this Account further prospers the field of intelligent stimuli-responsive discoloration materials and next-generation green displays.

Printable Off-On Thermoswitchable Fluorescent Materials for Programmable Thermally Controlled Full-Color Displays and Multiple Encryption.

Thermoswitchable fluorescent materials (TFMs) have received special attention due to their unique fluorescent colorimetric responses to temperature. Conventional TFMs generally display unicolor with switching from one color to another, showing unprintable and unsatisfied performances. These limitations greatly hinder their development and expansion toward advanced applications. Herein, the superior integration of full-color, off-on switching mode, printability, and high performance to TFMs is achieved successfully. The success is due to a thermally induced synchronous "dual/multichannel" stimulus-response mode regulated by a self-crystalline phase-change material; that is, synergistic changes of the molecular existence states and subsequent colors/spectra of the fluorescent modifier and fluorophores, accompanied by corresponding high-efficiency on-off switching of Förster resonance energy transfer. These TFMs are simple to prepare and show good performance, such as high fluorescence emission contrast (>100), great reversibility (>200 cycles), and easy-to-adjust response temperature. Particularly, these R/G/B TFMs can be prepared as tricolor fluorescent inks, and thus full-color emissions on flexible substrate can be easily obtained by printing. Finally, their great potential in switchable dynamic interior decoration, programmatic temperature-control information display, and senior information encryption are illustrated. This successful exploration offers a new perspective for designing and optimizing various other switchable materials with higher comprehensive performances.

Green revolution in electronic displays expected to ease energy and health crises.

The technological revolution of long-awaited energy-saving and vision-friendly displays represented by bistable display technology is coming. Here we discuss methods, challenges, and opportunities for implementing bistable displays in terms of molecular design, device structure, further expansion, and required criteria, hopefully benefiting the light-related community.

A Multiple Chirality Switching Device for Spatial Light Modulators.

A new and simple strategy towards electric-field-driven multiple chirality switching device has been designed and fabricated by combining a newly synthesized base-responsive chiroptical polymer switch (R-FLMA) and p-benzoquinone (p-BQ) via proton-coupled electron transfer (PCET) mechanism. Clear and stable triple chirality states (silence, positive, negative) of this device in visible band can be regulated reversibly (>1000 cycles) by adjusting voltage programs. Furthermore, such chiral switching phenomena are also accompanied by apparent changes of color and fluorescence. More importantly, the potential application of this device for a spatial light modulator has also been demonstrated.

Advances in nanomaterials for electrochromic devices.

Electrochromic devices (ECDs) have been regarded as promising candidates for energy-saving smart windows, next-generation displays and wearable electronics due to their significant benefits of simple and adjustable structures, low power consumption, flexible and stretchable features, and eye-friendly modes for displays. However, there are many existing issues waiting to be solved such as durability, reversibility and inadequate switching performances. These insurmountable technical bottlenecks significantly slow down the commercialization of next-generation ECDs. Nanomaterials with superior active reaction surface area have played indispensable roles in optimizing heterogeneous electron transfer and homogeneous ion transfer for ECDs and other optoelectronic devices. In recent years, with the joint efforts of various outstanding research teams, new kinds and methods for nanomaterials to fabricate ECDs with excellent performances have been rapidly developing. This review highlights the latest exciting results regarding the design and application of new and unique nanomaterials for each layer of ECDs. Meanwhile, the structures, mechanisms, features and preparation of the reported nanomaterials to improve the electrochromic properties have been discussed in detail. In addition, the remaining challenges and corresponding strategies of this field are also proposed. Hopefully, this review can inspire more and more researchers to enrich the nanomaterials for ECDs and other related fields to overcome faced technical barriers by innovative means and promote industrialization of ECDs and other optoelectronic technologies.

A Single-Pixel RGB Device in a Colorful Alphanumeric Electrofluorochromic Display.

With the rapid development of human society, consumer electronics have brought marvelous changes to human daily life, but they are accompanied by the much higher demand of display quality and visual experience. Therefore, ideal conversion among the three primary colors-red (R), green (G), and blue (B)-in a single pixel has been a better way to avoid the insurmountable technical barrier of subpixel technology of modern displays. Electrofluorochromic (EFC) materials capable of a novel luminescent switching, open a powerful way to design optoelectronic devices for displays and information storage etc. Colorful EFC devices, especially emitting the ideal three primary colors without subpixel technology, have been a challenge for years. Herein, a long-awaited single-pixel device with RGB color is fabricated successfully based on proton-coupled electron transfer. The RGB EFC device exhibits outstanding EFC properties, such as low turn-on voltage (+1.0 and -1.0 V), large color gamut, and good stability (500 cycles for each color). Prototypes of colorful alphanumeric displays are well demonstrated in a facile way. The success of this new exploration of single-pixel RGB EFC device not only provides the possibility of full-color emission in EFC devices, but also will widely broaden the EFC system and their applications.

A Transparent Multidimensional Electrode with Indium Tin Oxide Nanofibers and Gold Nanoparticles for Bistable Electrochromic Devices.

Due to the high energy efficiency and a wide range of potential applications in daily life, bistable electrochromic devices (BECDs) have gained extensive attention in recent years. However, poor bistability and slow response rate are the main barriers, which restrict the development of BECDs. Herein, a transparent multidimensional electrode with indium tin oxide (ITO) nanofibers and gold nanoparticles was fabricated to improve both the bistability and responsiveness of devices. Its criss-crossed ITO nanofibers with high length-to-diameter ratios to reduce the distance of heterogeneous electron transfer and its gold nanoparticles to form a stable Au-S bond to avoid self-erasing of electrochromic materials have been demonstrated and discussed systematically. This device based on the transparent multidimensional working electrode had a shorter response time (1/5) and a longer bistability (12/1) compared with the prototype devices based on common fluorine-doped tin oxide electrodes. Besides, this device had a promising electrochromic performance with a high coloration efficiency of 448.27 cm2/C and a switching stability with no significant attenuation after 1200 cycles.

A multicolour bistable electronic shelf label based on intramolecular proton-coupled electron transfer.

Bistable electrochromic materials have been explored as a viable alternative to reduce energy consumption in display applications. However, the development of ideal bistable electrochromic displays (especially multicolour displays) remains challenging due to the intrinsic limitations associated with existing electrochromic processes. Here, a bistable electrochromic device with good overall performance-including bistability (>52 h), reversibility (>12,000 cycles), colouration efficiency (≥1,240 cm2 C-1) and transmittance change (70%) with fast switching (≤1.5 s)-was designed and developed based on concerted intramolecular proton-coupled electron transfer. This approach was used to develop black, magenta, yellow and blue displays as well as a multicolour bistable electrochromic shelf label. The design principles derived from this unconventional exploration of concerted intramolecular proton-coupled electron transfer may also be useful in different optoelectronic applications.