Viologen-based flexible electrochromic devices

Electrochromic technology has gained significant attention in various fields such as displays,smart windows,biomedical monitoring,military camouflage,human-machine interaction,and electronic skin due to its ability to provide reversible and fast color changes under applied voltage.With the rapid development and increasing demand for flexible electronics,flexible electrochromic devices(FECDs)that offer smarter and more controllable light modulation hold great promise for practical applications.The electrochromic material(ECM)undergoing color changes during the electrochemical reactions is one of the key components in electrochromic devices.Among the ECMs,viologens,a family of organic small molecules with 1,1'-disubstituted-4,4'-dipyridinium salts,have garnered extensive research interest,due to their well-reversible redox reactions,excellent electron acceptance ability,and the ability to produce multiple colors.Notably,viologen-based FECDs demonstrate color changes in the liquid or semisolid electrolyte layer,eliminating the need for two solid electrodes and thus simplifying the device structure.Consequently,viologens offer significant potential for the development of FECDs with high optical contrast,fast response speed,and excellent stability.This review aims to provide a comprehensive overview of the progress and perspectives of viologen-based FECDs.It begins by summarizing the typical structure and recent exciting developments in viologen-based FECDs,along with their advantages and disadvantages.Furthermore,the review discusses recent advancements in FECDs with additional functionalities such as sensing,photochromism,and energy storage.Finally,the remaining challenges and potential research directions for the future of viologen-based FECDs are addressed.

A high-capacity viologen-based anolyte for high energy density neutral pH aqueous redox-flow batteries

Redox-flow batteries(RFBs)are a promising energy storage technology with remarkable scalability and safety for storing vast amounts of renewable energy and mitigating outputfluctuations of renewable power grids.We demonstrate a neutral pH aqueous RFB using a custom-designed 1’,1’’’,1’’’’’-(benzene-1,3,5-triyltris(methylene))tris(1-(3-(trimethyl ammonio)propyl)-[4’’,4’’’-bipyridine]-1,1’-diium)nonachloride(BTTMPB)as a 3 e-storage anolyte.The custom design with the high polarization in charge density has led to the excellent water solubility of 4.0 M in H_(2)O(321.6 A h L^(-1))and 2.4 M in 2.0 M NaCl(192.9 A h L^(-1)).The density functional theory(DFT)calculations and electrochemical experiments have shown 3 e-storage response of BTTMPB with a diffusion coefficient of 3.1×10^(-6)cm^(2) s^(-1)and rate con-stant of 1.6×10^(-2)cm s^(-1) for thefirst reduction process.The synthesized anolyte was paired with(Ferrocenylmethyl)trimethylammonium chloride(FcNCl)as catholyte enabling a 0.92 V aqueous RFB with 125.9 W h L^(-1)theoretical energy density.The aqueous RFB has an excellent cycling performance from 10-30 m A cm^(-2),energy efficiency up to 80%,capacity retention of 99.96%per cycle at 20 m A cm^(-2),and a high demonstrated energy density of 29.1 W h L^(-1).

A New Iodiplumbate-based Hybird Constructed from Asymmetric Viologen and Polyiodides：Structure,Properties and Photocatalytic Activity for the Degradation of Organic Dye

A new iodiplumbate/organic hybrid constructed from asymmetric viologen and polyiodides,（PBPY-H2）2[PbI4（I3）2]（1, PBPY = N-（propionate）-4,4？-bipyridinium）, has been synthesized via solvothermal reaction and structurally determined by X-ray diffraction method. Compound 1 crystallizes in monoclinic system, space group P21/c with Mr = 1936.72, a = 11.622（2）, b = 14.839（3）, c = 13.372（2）A^°, β = 109.447（3）°, V = 2174.6（7）A^°^3, Z = 2, Dc = 2.958 g/cm^3, F（000） = 1712, μ（Mo Kα） = 11.011 mm^–1, the final R = 0.0389 and wR = 0.0854 for 3866 observed reflections with I 〉 2σ（I）. [Pb I4（I3）2]^4-mononuclear cluster of 1 features a seldom example of coordinated I-3 donors for the lead center. Intermolecular hydrogen bonds between [Pb I4＋4（I3）2]^4-clusters and（PBPY-H）2^4＋ dimmers contribute to the formation of a 2-D layer. Its absorption spectrum was investigated, and lower energy band gap of 1.42 eV was explained by DFT calculation. Interestingly, 1 exhibits photocatalytic activity for the degradation of rhodamine B.

Design, Synthesis, Crystal Structure and Photophysical Properties of New Oxadiazole Extended Viologen Fluorophore

Viologens (N,N'-dimethyl-4,4-bipyridinium) are advanced functional materials, found important applications in electrochromic devices, molecular machines, organic batteries, and carbohydrate oxidation catalysts in alkaline fuel. In this article, we investigated the design, synthesis and photophysical properties of N,N'-dimethyl-2,5-Bis(pyridinium)oxadiazole 4 and its precursor 2,5- Bis(pyridine)oxadiazole 2. The crystal structure and photophysical properties of viologen 4 and precursor 2 have been determined. The viologen molecule 4 crystallized in monoclinic form, space group P21/n with four molecules in unit cell. Precursor molecule 2 also crystalized in monoclinic form, space group C2/c with four molecules in unit cell. From X-rd data, we found three cations in the molecular structure of viologen molecule 4, which is unusual in viologens. In the three-dimensional molecular packing diagram of molecule 4, the three cations and iodate anions are stabilized by C···C, C···I, N···I, N···H, H···I, N—H···I and C—H···I. The dihedral angle between planes having oxadiazole and two benzene rings are 5°and 8°, suggesting the molecule 4 is a slightly strained one. The molecular structure of precursor molecule 2 stabilized by C···C and N···H short contacts between the molecules. The molecule 4 displayed strong absorbance at 315 nm and emissions between 390 - 410 nm.

SYNTHESIS AND PHOTOCHROMISM OF ACRYLIC ESTER COPOLYMERS BEARING PENDANT VIOLOGEN GROUPS

A series of acrylic ester copolymers with viologen group as pendant were synthesizedthrough the reaction of MMA-EBA (Ethenyl bromoacetate) copolymer with 4-(4'-pyridyl)-N-alkyl (or arylalkyl) pyridiniums. These viologen copolymers can exchange their anionwith NH_4PF_6 in methanol to improve their solubility in organic solvents such as DMFand acetone. Compared with the corresponding low molecular viologens, these viologencopolymers have relatively lower color development rate under UV light and fade fasterin air due to less affinity to photo-reductant and deficiency of association between theircation radicals. Their photofatigue resistant ability is also slightly better than that of lowmolecular vinlogens.

Two electron utilization of methyl viologen anolyte in nonaqueous organic redox flow battery

Methyl viologen （MV） as a bench-mark anolyte material has been frequently applied in aqueous organic redox flow batteries （AORFBs） towards large-scale renewable energy storage. However, only the first re- duction of MV was utilized in aqueous electrolytes because of the insoluble MV0generated from the second reduction of MV. Herein, we report that methyl viologen with bis（trifluoromethane）sulfonamide counter anion, MVTFSI, can achieve two reversible reductions in a nonaqueous supporting elec- trolyte. Paired with （Ferrocenylmethyl）trimethylammonium bis（trifluoromethanesulfonyl）imide, FcNFFSI, as catholyte, the MVTFS/FcNTFSI nonaqueous organic redox flow battery （NOARFB） can take advantage of either one electron or two electron storage of the methyl viologen moiety and provide theoretical energy density of 24.9Wh/L and a cell voltage of up to 1.5V. Using a highly conductive LiTFSI/CH_3CN supporting electrolyte and a porous Daramic separator, the NOARFB displayed excellent cycling performance, includ- ing up to a 68.3g energy efficiency at 40 mA/cm2, and more than 88g total capacity retention after 100 cycles.

SELECTIVE REDUCTION OF NITROARENE MEDIATED BY AN INSOLUBLE RESIN WITH VIOLOGEN STRUCTURE AS ELECTRON-TRANSFER CATALYST

Abstract: : The substituted nitroarenes were reduced effectively to the corresponding aniline deriva tives by an insoluble resin with viologen structure as an electron-transfer catalyst(ETC) in dichloromethane-resin-water -three-phase system.

Preparation and Intramolecular Electron Transfer of A Covalently Linked Zinc Porphyrin-Methyl Viologen (MV^(2+)) Complex

Porphyrins and methyl viologen(MV;) are widely used as a photosensitizer and an electron acceptor respectively in photoinduced electron transfer systems. Literatures covered numerous examples of photochemical studies of porphyrins covalently linked to various electron acceptor units, such as viologen, which functioned as both a photosensitizer and an electron acceptor in the same molecule. However, the length of the linked chain between porphyrin and viologen is very important. To improve the rate of photoin-

A New Iodocuprate/methyl Viologen-based Hybird：Structure,Properties and Photocatalytic Activity for the Degradation of Organic Dye

A new copper iodide/organic hybrid incorporated with methyl viologen, [（MV）（Cu2I4）·H2O]n（1, MV = methyl viologen）, has been solvothermally synthesized and structurally determined by X-ray diffraction method. 1 crystallizes in tetragonal system, space group P42212 with Mr = 838.95, a = 12.4721（18）, c = 6.5892（13A, V = 1025.0（3） A3, Z = 2, Dc = 2.7125 g/cm3, F（000） = 756, μ（Mo Kα） = 8.097 mm–1, the final R = 0.0273 and wR = 0.0665 for 1062 observed reflections with I 〉 2σ（I）. In 1, the（Cu2I4）n2n- chain was constructed from edge-sharing of distorted Cu I4 tetrahedra. Its absorption spectrum and photoluminescence were investigated, and energy band gap of 1.76 e V indicates its semiconductor nature. Interestingly, 1 exhibits photocatalytic activity for the degradation of rhodamine B.

CATALYTIC DEBROMINATION OF DIPHENYL BROMOMETHANE UNDER HETEROPHASE CONDITIONS USING POLYMERS WITH VIOLOGEN STRUCTURE

The debromination of diphenyl bromomethane (Ph_2CHBr) using polymers with viologen structure as electron--transfer catalyst (ETC) afforded tetraphenylethane in good yields under het- erophase conditions.

EPR STUDIES ON THE DEBROMINATION OF DIPHENYL BROMOMETHANE IN THE PRESENCE OF VIOLOGEN DERIVATIVES AS ELECTRON-TRANSFER CATALYSTS (ETC)

The active intermediate'carbon radical' was detected by the spin—trapping reagent (POBN) during the debromination of Ph_2CHBr in the presence of viologen derivatives as electron—transfer catalysts(ETC).

Structures,Properties and Theoretical Studies on Two Viologen/Iodoargentate Supramolecular Hybrids

Two iodoargentate hybrids templated by viologen or viologen-like cations, i.e. [MV（Ag2I4）]n （1） and [MBYP（AgI2）]n （2）, （MV^2＋ = methyl viologen, MBYP^＋ = 1-methyl-2,2＇- bipyridine） have been synthesized in polar organic solvents. （Ag2I4）n^2- and （AgI2）n^2- chains in both compounds were constructed from edge-sharing of normal and distorted AgI4 tetrahedra, and a 2-D supramolecular layer based on C–H…I hydrogen bond was observed in 1. The band gaps of 1.54 and 2.67 eV indicated their semiconductor nature. Their band gap difference was led by different hydrogen bond donors in MV^2＋ and MBYP^＋, which result in more diffused p-π＊ antibonding orbitals in MV^2＋.

A bifunctional POM-based Cu-viologen complex with mixed octamolybdate clusters for rapid oxidation desulfurization and effective photogeneration of hydrogen

The design and synthesis of catalysts for the oxidation desulfurization and production of hydrogen are extremely important for solving environmental pollution and energy shortage.Herein,a novel bifunctional [α-Mo_(8)O_(26)]^(4-)/[β-Mo_(8)O_(26)]^(4-)-based Cu-viologen complex H_(4)[Cu_(2)~ⅠCl_(2)(Hbcbpy)_(4)] [α-Mo_(8)O_(26)] [β-Mo8O_(26)]·H_(2)O(BHU-2,Hbcbpy=1-(4-carboxybenzyl)-4,4'-bipyridinium) was synthesized and characterized by single-crystal X-ray diffraction(XRD),infrared radiation spectra,powder X-ray diffraction(PXRD) and X-ray photoelectron spectroscopy(XPS) spectra.The structural characteristic of BHU-2 is the presence of two types of octamolybdate clusters [α-Mo_(8)O_(26)]^(4-)/[β-Mo_(8)O_(26)]^(4-)and a new binuclear Cu~Ⅰ-Hbcbpy complex linked by Cl-bridges[Cu_(2)ⅠCl_(2)(Hbcbpy)_(4)]^(4+).BHU-2 as a heterogeneous catalyst exhibits excellent activities to the oxidation desulfurization and photocatalytic hydrogen production.At room temperature,BHU-2 can catalyze 96% conversion of methyl phenyl sulfide with 98% selectivity,and the process obeys the pseudo-first-order reaction kinetic with the half-life of9.6 min.The notorious 2-chloroethyl ethyl sulfide can achieve 99% conversion with 98% selectivity within only1 min at the presence of BHU-2,and the turnover frequency(TOF) is up to 7400 h^(-1).BHU-2 also exhibits high catalytic activity for the oxidation of other aromatic and aliphatic thioethers within short time at room temperature.Furthermore,BHU-2 shows a high catalytic activity for visible-light-driven hydrogen evolution with an H_(2) evolution rate of 1677.85 μmol·g^(-1)·h^(-1) within 10 h.Moreover,the catalytic activities do not decrease evidently after three cycles,revealing the prominent structural stability and recyclability.

Polymeric viologen-based electron transfer mediator for improving the photoelectrochemical water splitting on Sb_(2)Se_(3) photocathode

The photogenerated charge carrier separation and transportation of inside photocathodes can greatly influence the performance of photoelectrochemical(PEC)H2 production devices.Coupling TiO_(2) with p-type semiconductors to construct heterojunction structures is one of the most widely used strategies to facilitate charge separation and transportation.However,the band position of TiO_(2) could not perfectly match with all p-type semiconductors.Here,taking antimony selenide(Sb_(2)Se_(3))as an example,a rational strategy was developed by introducing a viologen electron transfer mediator(ETM)containing polymeric film(poly-1,1′-dially-[4,4′-bipyridine]-1,1′-diium,denoted as PV^(2+))at the interface between Sb_(2)Se_(3) and TiO_(2) to regulate the energy band alignment,which could inhibit the recombination of photogenerated charge carriers of interfaces.With Pt as a catalyst,the constructed Sb_(2)Se_(3)/PV^(2+)/TiO_(2)/Pt photocathode showed a superior PEC hydrogen generation activity with a photocurrent density of−18.6 mA cm^(-2) vs.a reversible hydrogen electrode(RHE)and a half-cell solar-to-hydrogen efficiency(HC-STH)of 1.54%at 0.17 V vs.RHE,which was much better than that of the related Sb_(2)Se_(3)/TiO_(2)/Pt photocathode without PV^(2+)(−9.8 mA cm^(-2),0.51%at 0.10 V vs.RHE).

Ultrastable Viologen Ionic Liquids-Based Ionogels for Visible Strain Sensor Integrated with Electrochromism,Electrofluorochromism,and Strain Sensing

Flexible electronics play a key role in the development of human society and our daily activities.Currently they are expected to revolutionize personal health management.However,it remains challenging to fabricate smart sensors with high robustness,reliability,and visible readout.Herein,high-performance electrochromic(EC),electro-fluorochromic(EFC),and double-network ionogels with excellent transmissivity,high mechanical robustness,and ultrastable reversibility are prepared by combination of thienoviologen-containing ionic liquids with poly(ethyl acrylate)elastomer.The ionogels exhibit good mechanical properties(1000%stretchability and 3.2 kJ m^(−2) fracture energy).The ionogel-based EC devices have a significantly simplified device fabrication process as well as superior cycling stability in which 88%of the contract ratio is maintained at 88%at 500 cycles,even after being stored for 2 years under ambient atmosphere(relative humidity:30%∼40%,25°C).The conductivity of ionogels showed a fast and reproducible response to strain,and the conductivity decreased with increased strain.By virtue of the EC and EFC properties of the thienoviologen component,the EC and EFC efficiency decreased with the increased strain loaded on the ionogels,and almost no EC or EFC phenomena were observed when the strain was above 300%.This feasible strategy provides an opportunity for the development of visible strain sensors to monitor the body’s movements through color and fluorescence emission.

Pyrene-tethered bismoviologens for visible light-induced C(sp^(3))-P and C(sp^(2))-P bonds formation

Developing efficient photosensitizers for C-P bond construction is highly important and remains a challenge due to the urgently needed for the synthesis of modified nucleosides,nucleotides,and other phosphine-containing ligands.Herein,two pyrene-tethered bismoviologen derivatives(Py-BiV^(2+))were designed and synthesized for visible-light-induced C-P bonds formation.The photochemical and electrochemical properties of Py-BiV^(2+)were studied systemically,certifying fine-tunable opto-electronic properties through the number of pyrene groups(4,n=1;6,n=2).The prepared Py-BiV^(2+)showed strong light absorption,while retaining good redox features and chromic response features that were inherent to viologens.4 exhibited accelerated photoinduced electron transfer in the presence of the electron donor(pyrene)and the generated 4(radical cation)showed higher stability.Accordingly,Py-BiV^(2+)directly served as photosensitizers for the first time in the visible-light-induced C(sp^(3))-P and C(sp^(2))-P bonds formation.As expected,these novel viologen derivatives exhibited good catalytic performance and good substrate expansibility under ambient conditions.

Viologens-based redox mediators with tunable HOMO–LUMO energy gap for highly effective hydrogen peroxide electrosynthesis

In comparison with the developing nano-carbon catalysts,some small organic molecules are also emerging as catalysts with typical features,however,their working mechanism is still unclear.Here,we synthesized a series of viologen-based heterogeneous catalysts with the same molecular skeleton but different substituent groups through anion exchange engineering.These viologen-based molecules were used as a model catalyst to investigate the underlying structure–function relationship for small molecules-based H_(2)O_(2) electrosynthesis.Differing from the commonly reported carbon-based electrocatalysts,viologens can produce H_(2)O_(2) in a synergistic manner,which means that viologens can not only directly catalyze oxygen reduction but also serve as a redox mediator.We found that the ring current and H_(2)O_(2) selectivity of viologens deliver an increasing trend with the increase of the alkyl chain length of alkyl-substituted viologens and further increase when using benzyl as the substituent group.As a result,a benzyl-substituted viologen(BV)delivers the best electrocatalytic performance among the samples,including the highest H_(2)O_(2) selectivity of 96.9%at 0.6 V and the largest ring current density of about 13.6 mA·mmol-1.Furthermore,density functional theory(DFT)calculations disclose that the carbon atoms bonded with positively charged N are the active sites and the small highest occupied molecular orbital(HOMO)–lowest unoccupied molecular orbital(LUMO)energy gap of BV is beneficial to the synergistic mechanism for H_(2)O_(2) production.This work sheds new insight into the efficient H_(2)O_(2) production in a synergistic manner for small molecules-based electrocatalysts.

4-氟苯乙酮双取代紫精的合成及光致变色特性

紫精材料在外界刺激(如光、热、电)下会表现出灵敏的变色行为,在光学开关和分子传感识别中具有良好的潜在应用前景.通过一步反应合成了4-氟苯乙酮双取代紫精衍生物(VioF_(2)·2Cl).氟苯乙酮取代基的引入扩大了其共轭体系,起到稳定自由基的作用,使着色更稳定持久.VioF_(2)·2Cl在紫外(ultraviolet,UV)灯的照射下可以快速地从白色转变为浅黄色直至黄绿色,显示出了灵敏的光致变色行为.变色后晶体中的VioF_(2)^(2+)分子间具有更短的π···π^(*)作用距离,能够促进光致电子转移(photoinduced electron transfer,PET)过程的发生,并且起到稳定紫精阳离子自由基的作用,使其能够在氧气环境下持续变色3 d而不被氧化褪色.这种新型的紫精衍生物表现出了更为灵敏的光致变色性能及自由基着色稳定性,在光致变色材料领域具有良好的潜在应用可能.

CdTe-paper-based Visual Sensor for Detecting Methyl Viologen

This study developed a method on detecting methyl viologen(paraquat)using a CdTe-paper-based visual sensor.The CdTe Qdots were immobilized on the paper using glycerin.The volume percentages of CdTe in glycerin were optimized to be 50%.The sensing principle is that the methyl viologen quenches the fluorescence intensity of CdTe Qdots in a concentration dependent manner.The sensor is linearly response to the logarithm concentration of the methyl viologen in the range from 0.39μmol/L to 3.89 mmol/L with a detection limit of 0.16μmol/L and the corre-lation coefficient R^(2) of 0.99.Three parallel experiments at the methyl viologen concentration of 38.89μmol/L give a relative error of 2.45%,which indicates a good reproducibility.The sensor is not disturbed by other pestisides in-cluding omethoate,anilofos,machete and glyphosate isopropylamine salt.The advantages of this sensor are dis-posable,stable,convenient,and easy to operate.

Viologen derivatives with extendedπ-conjugation structures:From supra-/molecular building blocks to organic porous materials

Recently,increasing atte ntion has been paid on extending theπ-conjugation structures ofviologens(1,1’-disubstituted-4,4’-bipyridylium salts)by incorporating planar aromatic units into the bipyridinium backbones.Various viologen derivative s with extendedπ-conjugation structures have been synthesized,including the N-termini aromatic substituted viologens,the extendedπ-conjugated viologens(denoted as ECVs)as well as theπ-conjugated oligomeric viologens(denoted as COVs).These compounds typically exhibit interesting properties distinguished from those of an isolated viologen unit,which make them as new class of electron deficient supra-/molecular building blocks in supramolecular chemistry and materials science.In this review,we would like to highlight the recent advances of viologen derivatives with extendedπ-conjugation structures in versatile applications ranging from electrochromic and energy storage materials,the ECV/COV-based supramolecular self-assembly systems including the linear supramolecular polymers and 2D/3D supramolecular organic frameworks(SOFs),to the viologen-based covalent organic frameworks(COFs)/networks.We hope this review will serve as an in-time summary worthy of referring,more importantly,to provide inspiration in the rational design of novel molecules with unexplored properties and functions.