Viologen-based Polymers Research Articles

Polypeptide-based batteries toward sustainable and cyclic manufacturing

Polypeptide-based batteries toward sustainable and cyclic manufacturing

Extending the Color Retention of an Electrochromic Device by Immobilizing Color Switching and Ion-Storage Complementary Layers

The thermal polymerization of a bis(triphenylamine)-bis(styrene) monomer on ITO coated glass gave an electroactive film that underwent two stepwise oxidations. The perceived color change of the film upon stepwise oxidation was colorless-to-yellow followed by yellow-to-blue. The anodic cyclic voltammogram of the monomer was consistent over multiple cycles. The immobilized film could be reversibly switched between its colorless and blue states with applied potential in both a half- and full-electrochromic functioning device. The devices could also reversibly switch their colors upwards of 6 h. The retention of the electrochemically induced blue color was contingent on the device architecture. Upwards of 80% of the color was maintained 30 min after the potential was turned off with the double-layer electrochromic device structure. This device was prepared from two electroactive layers: a bis(triphenylamine) and viologen-based polymers that were immobilized on the electrodes. In contrast, 50% of the color of the active electrochromic device that was prepared from a single electroactive layer bleached 7 min once the potential was no longer applied.

Viologen-Based Electrochromic Materials: From Small Molecules, Polymers and Composites to Their Applications.

Organic materials have gained considerable attention for electrochromic (EC) applications owing to improved EC performance and good processability. As a class of well-recognized organic EC materials, viologens have received persistent attention due to the structural versatility and property tunability, and are major active EC components for most of the marketed EC devices. Over the past two decades, extensive efforts have been made to design and synthesize different types of viologen-based materials with enhanced EC properties. This review summarizes chemical structures, preparation and EC properties of various latest viologen-based electrochromes, including small viologen derivatives, main-chain viologen-based polymers, conjugated polymers with viologen side-chains and viologen-based organic/inorganic composites. The performance enhancement mechanisms are concisely discussed. The current marketed viologens-based electrochromic devices (ECDs) are briefly introduced and an outlook on the challenges and future exploration directions for viologen-based materials and their ECDs are also proposed.

X-ray and UV Dual Photochromism, Thermochromism, Electrochromism, and Amine-Selective Chemochromism in an Anderson-like Zn7 Cluster-Based 7-Fold Interpenetrated Framework.

Smart materials are highly desirable over the recent decade due to the growing demand of complicated nature. Stable stimuli-responsive smart materials exhibit widespread potential for applications in smart windows, sensors, separators, chemical valves, and release platforms but are rare. Despite being good candidates, viologen-based multifunctional smart materials are still a challenging task for chemists. To obtain such materials, the judicious strategy is to introduce polynuclear metal-carboxylate clusters as electron donors into a stable framework to increase chromic sensitivity. Toward this endeavor, we have synthesized a novel viologen-based polymer with a unique Anderson-like metal-carboxylate cluster, [Zn7(bpybc)3(o-BDC)6]·2NO3·6H2O (bpybc = 1,1'-bis(4-carboxyphenyl)-4,4'-bipyridinium, o-BDC = o-benzenedicarboylic acid) (1), which is a particular 7-fold interpenetrated framework with a 3D pcu network in which bpybc ligand as the linker and Zn7O30C12 as the second building unit (Zn7 SBU) were used as 6-connected nodes. More importantly, it shows excellent chromic behavior in response to multiple external stimuli especially soft X-ray and UV dual light, temperature, electricity, and organic amines, which stand out in the viologen-based polymers. Interestingly, the coloration process of 1 from "core" to "edge" is observed upon heating at the appropriate temperature, which has not yet been found in other reported thermochromic materials. Of particular interest for 1 is the couple of quaternary stimuli-sensitive abilities because it simultaneously meets the following conditions: (i) the capability of withstanding high light, higher temperature, extreme pH, and other harsh conditions; and (ii) the high sensitivity to external stimuli keeping away from photodegradation, thermal relaxation, side reactions, and so on. To be noted, 1 has high thermal stability and chemical stability, which are excellent advantages as smart materials. To further develop possible practical utilization, 1 has been doped into the polymer matrixes to construct a hybrid film, which not only keeps the response to external stimuli but also significantly improves the repeatability of the photochromic process, indicating that a new smart device with multi-stimuli-responsive functions will emerge successively in the future.

Photolithographically-Patterned Electroactive Films and Electrochemically Modulated Diffraction Gratings

This manuscript presents an overview of work directed toward the creation of arbitrary micron-scale patterns of electroactive polymer films by the application of photolithography. A brief overview of work by other groups in the field is followed by a detailed description of work from our own labs which resulted in the development of methods to pattern a variety of different electroactive materials, including Ru− and Os−polypyridine complexes, viologen-based polymers, and a low-potential polythiophene. The discussion provides detail on the photolithographic methodology. In addition, the spatially-patterned films are characterized by using optical and scanning electron microscopy. The voltammetric and spectroelectrochemical properties of several of the lithographically-patterned films are also presented. Finally, photolithography is applied to fabricate electrochromic optical diffraction gratings. The diffraction efficiency of these electroactive gratings can be modulated by an electrochemical stimulus. The properties and mechanism for operation of the electrochromic gratings are described.