Ultra-Stable High-Capacity Polythiophene Derivative for Wide-Potential-Window Supercapacitors.

Conducting polymer (CP)-based supercapacitors show great promise for applications in the field of wearable and portable electronics. However, these supercapacitors face persistent challenges, notably low energy density and inadequate stability. In this study, we introduce a polythiophene derivative, designated as poly(EPE), synthesized via the electrochemical polymerization of 8-bis(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)-3,3-dimethyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepine (EPE). The resulting poly(EPE) polymer exhibits an exemplary 3D porous network-like structure, significantly enhancing its capacitance performance. When employed as the electrode material, the symmetric supercapacitor demonstrates an exceptionally high specific capacitance of 1342 F g-1 at a current density of 4.0 A g-1, along with impressive energy and power densities of 119.3 W h kg-1 and 38.83 kW kg-1, respectively. These capacitance values surpass those of previously reported pristine CP-based supercapacitors. Notably, the supercapacitor showcases outstanding stability, maintaining a retention rate of 92.5% even after 50,000 charge-discharge cycles. These findings underscore the substantial potential of poly(EPE) as an electrode material for the advancement of the supercapacitor technology.

Large-fused-ring-based D-A type electrochromic polymer with magenta/yellowish green/cyan three-color transitions.

Large-fused-ring-based conjugated polymers possess wide application prospects in optoelectronic devices due to their high charge transport and wide optical absorption. In this paper, three low-bandgap donor-acceptor (D-A) type polymers PBIT-X (X = 1, 2, 3) based on alkylated benzodithiophene and tris(thienothiophene) as donors and thiadiazol-quinoxaline as an acceptor were synthesized via Stille coupling polymerization at different (donor/acceptor) D/A molar feed ratios. The band gaps of PBIT-1, PBIT-2, PBIT-3 were 1.10 eV, 1.04 eV and 1.02 eV, respectively. Spectroelectrochemistry studies showed that the three D-A type polymers have dual bands located in visible and near-infrared regions in the neutral state. The three D-A type polymers possess good electrochromic properties, such as an optical contrast of 56% and response time of 0.3 s. In particular, PBIT-3 could achieve three color changes from magenta to yellowish green to cyan during the oxidation process. The results indicate that these D-A type conjugated polymers based on large fused-ring units exhibit multiple color changes, endowing them with huge potential applications in visible and near-infrared electrochromic devices.

Toward High-Performance Electrochromic Conjugated Polymers: Influence of Local Chemical Environment and Side-Chain Engineering.

Three homologous electrochromic conjugated polymers, each containing an asymmetric building block but decorated with distinct alkyl chains, were designed and synthesized using electrochemical polymerization in this study. The corresponding monomers, namely T610FBTT810, DT6FBT, and DT48FBT, comprise the same backbone structure, i.e., an asymmetric 5-fluorobenzo[c][1,2,5]thiadiazole unit substituted by two thiophene terminals, but were decorated with different types of alkyl chain (hexyl, 2-butyloctyl, 2-hexyldecyl, or 2-octyldecyl). The effects of the side-chain structure and asymmetric repeating unit on the optical absorption, electrochemistry, morphology, and electrochromic properties were investigated comparatively. It was found that the electrochromism conjugated polymer, originating from DT6FBT with the shortest and linear alkyl chain, exhibits the best electrochromic performance with a 25% optical contrast ratio and a 0.3 s response time. The flexible electrochromic device of PDT6FBT achieved reversible colors of navy and cyan between the neutral and oxidized states, consistent with the non-device phenomenon. These results demonstrate that subtle modification of the side chain is able to change the electrochromic properties of conjugated polymers.

Effect of the cross-linker length of thiophene units on photocatalytic hydrogen production of triazine-based conjugated microporous polymers.

Conjugated microporous polymers (CMPs) have been investigated in the field of photocatalytic hydrogen production because of their extended π-conjugation, tunable chemical structure and excellent thermal stability. Herein, we construct three CMPs based on thiophenes and triazine, and prove the effect of cross-linker length on photocatalytic activity of CMPs. BTPT-CMP1 exhibits blue-shifted optical absorption compared to BTPT-CMP2 and BTPT-CMP3 with long cross-linkers, however, possesses higher photocurrent because of the large specific surface area and small interface charge transfer resistance of BTPT-CMP1. It was found that BTPT-CMP1 (5561.87 µmol g-1 h-1) with short cross-linkers exhibits better photocatalytic performance compared to BTPT-CMP2 (1840.86 µmol g-1 h-1) and BTPT-CMP3 (1600.48 µmol g-1 h-1). Also, BTPT-CMP1 possesses a higher hydrogen evolution rate than most reported 1,3,5-triazine based conjugated polymers. These results demonstrate that the cross-linker length has great influence on the photocatalytic properties of conjugated microporous polymers, which offers theoretical direction for designing high-performance CMPs.

Electrochromic polymers with multiple redox couples applied to monitor energy storage states of supercapacitors.

Two electrochromic polymers based on thiophene-benzene derivatives were prepared using an electrochemical method and exhibited multiple separate redox couples due to the introduction of side chains. The energy storage states of electrochromic supercapacitors based on the resulting polymers could be monitored by their appearance colour.

Fluoro-Modulated Molecular Geometry in Diketopyrrolopyrrole-Based Low-Bandgap Copolymers for Tuning the Photovoltaic Performance.

Fluorination of conjugated polymers is an effective strategy to tune the energy levels for obtaining high power conversion efficiency (PCE) in organic solar cells. In this work, we have developed fluoro-modulated molecular geometries in diketopyrrolopyrrole based low-bandgap copolymers. In these polymers, planar conformation can be locked by intramolecular non-covalent interaction (intramolecular supramolecular interaction) between the sulfur atoms and the introduced F atoms (F···S interaction). By varying the fluorinated moieties, such a planarity can be disturbed and the molecular geometry is tuned. As a result, the polymer' properties can be modulated, including the ultraviolet-visible absorption spectrum to become broaden, charge mobility to be enhanced, open-circuit voltage (V oc) and short-circuited current (J sc) to be elevated, and thus photovoltaic performance to be improved. The photovoltaic device based on PCFB, one of the fluorinated terpolymers, exhibited a high PCE near 8.5% with simultaneously enhanced V oc and J sc relative to the non-fluorinated one (PCB).

Impact of the Bonding Sites at the Inner or Outer π-Bridged Positions for Non-Fullerene Acceptors.

Two A-π-D-π-A-type non-fullerene acceptors (IDT-ToFIC and IDT-TiFIC) with 5-hexylthienyl chains substituted at the inner and outer ß-positions of the thiophene π-bridge have been designed, respectively. Impacts of varied positional modifications are systematically studied. By utilizing PBDB-T as the donor, polymer solar cells are constructed with these two molecules as acceptors. Power conversion efficiencies of 11.09 and 9.46% are acquired for IDT-ToFIC- and IDT-TiFIC-based devices, respectively. Our studies have demonstrated that the use of thiophene spacers carrying one conjugated side chain at different positions can markedly enhance the photovoltaic properties relative to the corresponding control molecule IDTT2F.

Controlling Molecular Packing and Orientation via Constructing a Ladder-Type Electron Acceptor with Asymmetric Substituents for Thick-Film Nonfullerene Solar Cells.

A nonfullerene acceptor, IDTT-OB, employing indacenodithieno[3,2- b]thiophene (IDTT) decorated with asymmetric substituents as the core, is designedly prepared. In comparison with the analogue IDT-OB, extending the five-heterocyclic indacenodithiophene (IDT) core to seven-heterocyclic fused ring endows IDTT-OB with more broad absorption and elevated highest occupied molecular orbital energy level. In addition, IDTT-OB shows a more intense molecular packing and a higher crystalline behavior with a strong face-on orientation in the neat film and the PBDB-T:IDTT-OB blend film. Furthermore, an ideal nanomorphology with a domain size of 19 nm can be obtained, which is in favor of exciton diffusion and charge separation. Accordingly, PBDB-T:IDTT-OB-based polymer solar cells demonstrate a maximum power conversion efficiency (PCEmax) of 11.19% with an impressive fill factor of 0.74, comparable to the state-of-the-art acceptors with similar molecular backbones. More importantly, IDTT-OB-based devices show good tolerance to the film thickness, which maintain a high PCE of 10.20% with a 250 nm thick active layer, demonstrating that the asymmetric acceptor is profound for fabricating high-efficiency thick-film nonfullerene solar cells.

A simple strategy to achieve shape control of Au-Cu2-xS colloidal heterostructured nanocrystals and their preliminary use in organic photovoltaics.

Au-Cu2-xS Janus nanostructures with a shape-controlled semiconductor part are successfully built. The key parameters for controlling the morphology of Cu2-xS in Au-Cu2-xS are demonstrated. Coupled local surface plasmon resonance (LSPR) properties in these Au-Cu2-xS NCs give them potential for application in polymer solar cells (PSCs) as an efficient dopant.

Highly sensitive "turn-on" fluorescent chemical sensor for trace analysis of Cr3+ using electro-synthesized poly(N-(9-fluorenylmethoxycarbonyl)-l-histidine).

Trivalent chromium (Cr3+) can cause severely environment pollution, declining quality of edible agro-products in plants and animals, and human diseases. Poly(N-(9-fluorenylmethoxycarbonyl)-l-histidine) (PFLH) synthesized by the direct electro-polymerization of its corresponding commercially available monomer in both boron trifluoride diethyl etherate and dichloromethane mixed system. The "turn-on" type fluorescent sensor based on PFLH displayed high sensitivity and selectivity for Cr3+ detecting. The structure of PFLH was rationally proved by 1H NMR spectra, FT-IR spectra, quantum chemical calculations, and its optical properties were characterized. The electro-synthesized PFLH exhibited a "turn-on" fluorescent response towards Cr3+, which was employed as a sensing platform for the "turn-on" fluorescent analysis of Cr3+ in a wide linear range from 5.1nM to 25µM with a low limit of detection as low as 1.7nM. The possible mechanism of fluorescent "turn-on" sensor based on PFLH for Cr3+ was proposed. The sensor displayed high sensitivity, good selectivity, satisfactory practicability, suggesting that PFLH has potential fluorescent application for "turn-on" sensing Cr3+ in agricultural environments and edible agro-products of plants and animals.

Solvent effects on electrosynthesis, morphological and electrochromic properties of a nitrogen analog of PEDOT.

A new nitrogen analog of 3,4-ethylenedioxythiophene (EDOT), N-methyl-3,4-dihydrothieno[3,4-b][1,4]oxazine (MDTO), was electropolymerized in different solvents (deionized water, acetonitrile, and propylene carbonate) using LiClO4 as the electrolyte. The structure and performance of as-prepared PMDTO polymers were systematically studied by cyclic voltammetry, UV-vis spectroscopy, FT-IR, SEM, thermogravimetry, spectroelectrochemistry and electrochromic techniques. To our surprise, solvents had a major influence on the electropolymerization of MDTO and properties of the resultant polymers, including morphology, electrochemistry, electronic and optical properties, and electrochromics, etc. In aqueous solution, MDTO revealed the lowest onset oxidation potential (0.19 V) than in acetonitrile (0.48 V) and propylene carbonate (0.49 V). However, PMDTO films showed rather poor cycling stability in water, while outstanding stability in acetonitrile and propylene carbonate. Films prepared in propylene carbonate displayed a rather smooth morphology, lower band gap (1.65 eV), higher transparency (97.3%) and a contrast ratio (44.6%) at λ = 466 nm. PMDTO films obtained in acetonitrile showed significantly higher coloration efficiency (169.5 cm(2) C(-1)) than in other two solvents (∼ 97.6 cm(2) C(-1)) with a moderate contrast ratio (24.5%).

Thiadiazolo[3,4-c]pyridine as an Acceptor toward Fast-Switching Green Donor-Acceptor-Type Electrochromic Polymer with Low Bandgap.

Thiadiazolo[3,4-c]pyridine (PT), an important analog of benzothiadiazole (BT), has most recently been explored as a novel electron acceptor. It exhibits more electron-accepting ability and other unique properties and potential advantages over BT, thus inspiring us to investigate PT-based donor-acceptor-type (D-A) conjugated polymer in electrochromics. Herein, PT was employed for the rational design of novel donor-acceptor-type systems to yield a neutral green electrochromic polymer poly(4,7-di(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)-[1,2,5] thiadiazolo[3,4-c]pyridine) (PEPTE). PEPTE revealed a lower bandgap (Eg,ele=0.85 eV, Eg,opt=1.12 eV) than its BT analog and also favorable redox activity and stability. Furthermore, electrochromic kinetic studies demonstrated that PEPTE displayed higher coloration efficiency than BT analog, good optical memory, and very fast switching time (0.3 s at all three wavelengths), indicating that PT would probably be a promising choice for developing novel neutral green electrochromic polymers by matching with various donor units.