热处理WO3电变色膜稳定性研究

采用电子束蒸发淀积ＷＯ３薄膜。根据已有的ＷＯ３薄膜脱水过程结论而选择适当温度对薄膜进行退火处理。在大量含水的和不含水的两类Ｌｉ＾＋电解质中进行比较性着色和消色循环实验，表明在２９０℃以下热退火处理能明显增加ＷＯ３薄膜在含水 电解质中的循环寿命。     

Multi‐input–Multi‐output Molecular Response System Based on Dynamic Redox Behavior of Hexaphenylethane‐type Electron Donors with the Tetrahydrophenanthrazepine Skeleton: Strong Chiroptical Signals through the Transmission of Point Chirality to Helicity

The title heterocyclic donors undergo reversible C? C bond formation/cleavage upon electron transfer (dynamic redox behavior). The helical sense in both neutral and cationic states is interconvertible by facile ring flipping. The π‐type asymmetric center on the azepine nitrogen atom induces a significant degree of diasteromeric preference, thus endowing strong CD activity based on exciton coupling. Chiroptical properties could be modified not only by redox reactions but also by heat and protonation. The present redox pairs can serve as unprecedented three‐way‐input (e, H⁺, Δ) and two‐way‐output (UV/Vis, CD) response systems.     

A Dual-Mode Electrochromic Platform Integrating Zinc Anode-Based and Rocking-Chair Electrochromic Devices

The complementary electrochromic device, where the optical transmittance changes upon the flow of cations back and forth between anodic and cathodic electrodes, operates in a rocking-chair fashion if it can inherently self-discharge. Herein, the first demonstration of a dual-mode electrochromic platform having self-coloring and self-bleaching characteristics is reported, which is realized by sandwiching zinc metal within a newly-designed Prussian blue (PB)-WO₃ rocking-chair type electrochromic device. It is demonstrated that the redox potential differences between the zinc metal and the WO₃/PB electrodes endow the self-color-switching of these electrodes. By employing a hybrid electrolyte of Zn²⁺/K⁺, it is further shown that the colored PB-WO₃ rocking-chair device is capable of spontaneously bleaching when the anodic and cathodic electrodes are coupled. This dual-mode light-control strategy enables the electrochromic devices to exhibit four distinct optical states with the highest optical contrast of 72.6% and fast switching times (<5 s for the bleaching/coloration processes). Furthermore, the built-in voltage of the dual-mode electrochromic devices not only promotes energy efficiency, but also augments the bistability of the devices. It is envisioned that the broad implication of the present platform is in the development of self-powered smart windows, colorful displays, optoelectronic switches, and optical sensors.     

Electrochromic nickel oxide films made by reactive r.f. sputtering from different targets

We describe the preparation and optical–electrical characterization of thin electrochromic layers based on nickel oxide (NiO_x). These layers were deposited by reactive radiofrequency (r.f.) sputtering from nickel or nickel oxide targets, maintaining the r.f. power and varying the oxygen flow in a gas mixture of Ar and O₂ from 5% up to 30%. The Ni/O ratio in the deposited thin films was determined by Rutherford backscattering spectroscopy (RBS) and the microstructure was investigated by x‐ray diffraction. The deposition rate was found to be strongly dependent on the type of target used. The electrochromic behaviour in aqueous alkaline electrolyte (0.1 N KOH solution) was investigated by electrochemical cyclization. Samples deposited by the NiO target exhibited the lowest N/O ratio (0.5) and the highest value of intercalated charge (～4.9 × 10^?2 mC cm^?2 nm^?1). Among the same samples the highest value of the intercalated charge was found for those deposited at low oxygen flow, but these samples exhibit the smallest reversible changes in optical absorption in the wavelength range 330–1200 nm. Samples deposited by the nickel target do not exhibit significant variations in the value of the exchanged charge; the measured Ni/O ratio indicates a stoichiometry closer to NiO. We also observed the switching behaviour by analysing the films in cyclic time mode at a fixed wavelength. The commutation response time is estimated by measurement under the application of a step waveform potential. Copyright © 2004 John Wiley & Sons, Ltd.     

ELECTROCHEMICAL POLYMERIZATION OF ANILINE IN PHOSPHORIC ACID AND THE PROPERTIES OF POLYANILINE

The behavior of the electrochemical polymerization of aniline in a weak acid, phosphoric acid, is very similar to that in strong acids, i.e. its polymerization rate increases quickly with the electrolysis time. The FTIR spectra of polyaniline samples synthesized in phosphoric acid indicate that the counter ion H2PO4^- is present in both the oxidized form and the reduced form of polyaniline. The counter ion plays an important role in adjusting the pH value at the electrode surface of polyaniline during the oxidation and reduction processes. As a result, a pair of redox peaks still appear in cyclic voltammograms of polyaniline in a solution of sodium sulfate of pH 5.5 and in a solution of NaH2PO4 of pH 7.0,respectively, at low potential scan rate; and the color of polyaniline film also changes with applied potential at pH 7.0. Thus,the pH region for the electrochemical activity and the electrochromism of polyaniline is extended to pH 5.5 for a solution of sodium sulfate and to pH 7.0 for a solution of NaH2PO4. The conductivity of polyaniline is 3.3 S cm^-1, depending on the concentration of phosphoric acid used in the stage of polymerization of aniline. The result of elemental analysis of polyaniline is presented here.     

Thieno[3,2‐b]Thiophene End‐Capped all‐Sulfur Analog of 3,4‐Ethylenedioxythiophene and its Eletrosynthesized Polymer: Is Distorted Conformation Not Suitable for Electrochromism?

By employing planar thieno[3,2‐b]thiophene (TT) as end‐capped units and famous 3,4‐ethylenedioxythiophene (EDOT) or its all‐sulfur analog 3,4‐ethylenedithiathiophene (EDTT) as cores, two conjugated oligomer, TT‐EDOT‐TT and TT‐EDTT‐TT, have been synthesized and electropolymerized into electrochromic polymer films, P(TT‐EDOT‐TT) and P(TT‐EDTT‐TT), respectively. Due to strongly noncovalent inter/intramolecular interactions from S? S attraction of TT‐EDTT‐TT, it has twisted molecular configuration in contrast to planar TT‐EDOT‐TT. Spectroscopic, electrochemical, morphological as well as theoretical calculation studies of these oligomers or polymers were carried out to reveal the significant influence of such molecular geometry on their physicochemical and optoelectronic properties. According to electrochromic kinetics, P(TT‐EDTT‐TT) presented preferable electrochromic behavior such as the higher optical contrast (70.8%), favorable coloration efficiency (331.3 cm² C^?1) and fast response time (0.72 s). This research will help us deeply understand the effect of spatial organization of precursor molecules on the properties of electrochromic polymers and provides a promising strategy to develop high‐performance electrochromic materials. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 1041–1048     

旋涂法制备WO3薄膜电致变色性能

"智能窗"大规模推广顺应可持续发展潮流,三氧化钨(WO_3)是生产"智能窗"的一种重要电致变色材料,但调控WO_3薄膜电致变色性能机制仍待进一步研究。采用旋涂法制备WO_3薄膜,重点研究了溶液浓度和旋涂次数对调控WO_3薄膜电致变色性能的影响。通过表面轮廓仪测量薄膜厚度,X射线衍射(XRD)测量薄膜结晶情况,原子力显微镜(AFM)和扫描电子显微镜(SEM)分析薄膜表面形貌,光谱仪测量薄膜初始态、着色态和褪色态的透射率。实验结果表明,随着溶液浓度增加(0. 2～1. 0 mol/L),薄膜厚度从9. 7 nm增加到33. 3 nm,透射率调制能力从0%提升到37. 0%;多次旋涂薄膜厚度线性增长,线性拟合优度(R~2)达0. 98,5次旋涂后透射率调制能力达51. 3%。改变溶液浓度和旋涂次数都是调控薄膜透射率调制能力的有效手段,精准调控薄膜透射率调制能力对设计不同应用场景的电致变色器件具有重大意义。     

Redox‐Active Tetraruthenium Macrocycles Built from 1,4‐Divinylphenylene‐Bridged Diruthenium Complexes

Metallamacrocylic tetraruthenium complexes were generated by treatment of 1,4‐divinylphenylene‐bridged diruthenium complexes with functionalized 1,3‐benzene dicarboxylic acids and characterized by HR ESI‐MS and multinuclear NMR spectroscopy. Every divinylphenylene diruthenium subunit is oxidized in two consecutive one‐electron steps with half‐wave potential splittings in the range of 250 to 330 mV. Additional, smaller redox‐splittings between the +/2+ and 0/+ and the 3+/4+ and 2+/3+ redox processes, corresponding to the first and the second oxidations of every divinylphenylene diruthenium entity, are due to electrostatic effects. The lack of electronic coupling through bond or through space is explained by the nodal properties of the relevant molecular orbitals and the lateral side‐by‐side arrangement of the divinylphenylene linkers. The polyelectrochromic behavior of the divinylphenylene diruthenium precursors is retained and even amplified in these metallamacrocyclic structures. EPR studies down to T=4 K indicate that the dications 1‐H²⁺ and 1‐OBu²⁺ are paramagnetic. The dications and the tetracation of macrocycle 3‐H display intense (dications) or weak ( 3‐H⁴⁺ ) EPR signals. Quantum chemical calculations indicate that the four most stable conformers of the macrocycles are largely devoid of strain. Bond parameters, energies as well as charge and spin density distributions of model macrocycle 5‐H^Me were calculated for the different charge and spin states.     

Solution‐processable transmissive‐to‐green switching electrochromic polyamides bearing 2,7‐bis(diphenylamino)naphthalene units

A new 2,7‐bis(diphenylamino)naphthalene‐based diamine monomer, N,N′‐bis(4‐aminophenyl)‐N,N′‐bis(4‐methoxyphenyl)‐2,7‐naphthalenediamine, was synthesized and polymerized with various aromatic dicarboxylic acids via the phosphorylation polyamidation reaction leading to a new series of redox‐active and electrochromic aromatic polyamides. The polyamides exhibited high solubility in many polar aprotic solvents, good film‐forming ability, and high thermal stability. They also showed stable electrochemical stability and anodically green coloring when oxidized. The two arylamino centers showed a weak electronic interaction via the 2,7‐naphthalenediyl bridge, and thus they started to oxidize almost at the same time. No intervalence charge transfer (IVCT) absorption was observed during the oxidation processes of these polyamides. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 1409–1421     

Multifunctional triphenylamine polymers synthesized via direct (hetero) arylation polymerization

The design rules for creating multifunctional organic electronic materials are currently limited. By copolymerizing twisted triphenylamine (TPA) and electron rich dioxythiophene (XDOT) monomers via Direct (Hetero) Arylation Polymerization (DHAP), a set of polymers are obtained that perform as yellow to transmissive electrochromic (EC) films with up to 45% contrast, as well as in electroluminescent (EL) applications, achieving a luminance of ∼450 cd/m² in yellow‐green polymer light‐emitting diodes (PLEDs). In addition, polymerizing TPA with a donor‐acceptor‐donor monomer results in a low‐bandgap polymer that achieves power conversion efficiencies up to 2.5% when blended with PC₇₁BM in conventional organic photovoltaic (OPV) devices. Incorporation of TPA units into the polymer backbone largely breaks any aggregation and ordering in the solid‐state, leading to highly soluble materials that form smooth, reproducible thin films. The TPA unit also serves to break conjugation throughout the polymer backbone, providing precise control over optical and electronic properties through choice of comonomer. These results suggest that TPA copolymers can be useful for achieving multi‐functionality without sacrificing facile solution processability, making them promising candidates for multifunctional devices like dual EC/EL displays. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 147–153