Organic electrochromic materials change color rapidly under applied potential. A butterfly‐shaped compound, 5,5′,‐5″,‐5′″‐(thieno[3,2‐b]thiophene‐2,3,5,6‐tetrayl) tetrakis‐(2,3‐dihydrothieno[3,4‐b][1,4]dioxine) (t‐EDOT‐TT) is synthesized for the first time and polymerized at different potentials via electropolymerization technique. By applying different polymerization potentials, the optical and electrochromic properties of this newly synthesized polymer can be tuned. Owing to the dependence of functional group position in the polymer structure on the redox potential, this polymer can be utilized in very interesting organic optoelectronic applications.
Here, a conjugated polymer VTTPD based on thieno[3,4‐c]pyrrole‐4,6‐dione (TPD) and dithiophene with vinyl as linker is synthesized and characterized. Electrochemical and optical studies indicate the LUMO and HOMO energies of the polymer are −3.70 and −5.39 eV. Theoretical calculation with density functional theory suggests that H‐bonds are formed between the TPD carbonyl (O) and its neighboring vinyl (H) which benefit the planarity and π‐conjugation of the polymer backbone. Bottom contact bottom gate organic field effect transistor devices based on VTTPD are fabricated and examined in air. After annealing at 160 °C, the devices exhibit excellent performance of μh = 0.4 cm2 V−1 s−1, Ion/off = 106, Vth within −10 V to −5 V. Thin film morphologies before and after the annealing process are also investigated with XRD and AFM.
Systematic optimization of the chemical structure of wide‐bandgap (≈2.0 eV) “donor–acceptor” copolymers consisting of indacenodithiophene or indacenodithieno[3,2‐b ]thiophene as the electron‐rich unit and thieno[3,4‐c ]pyrrole‐4,6‐dione as the electron‐deficient moiety in terms of alkyl side chain engineering and distance of the electron‐rich and electron‐deficient monomers within the repeat unit of the polymer chain results in high‐performance electron donor materials for organic photovoltaics. Specifically, preliminary results demonstrate extremely high open circuit voltages (V ocs) of ≈1.0 V, reasonable short circuit current density (J sc) of around 11 mA cm−2, and moderate fill factors resulting in efficiencies close to 6%. All the devices are fabricated in an inverted architecture with the photoactive layer processed by doctor blade equipment, showing the compatibility with roll‐to‐roll large‐scale manufacturing processes. From the correlation of the chemical structure—optoelectronic properties—photovoltaic performance, a rational guide toward further optimization of the chemical structure in this family of copolymers, has been achieved.
Pentacyclic lactam acceptor unit TPTI invented by our group is proved to be a good building block for efficient D‐A copolymers used in organic solar cells. Here, two D‐A copolymers PBTTPTI and PTTTPTI are developed by copolymerizing TPTI with 2,2′‐bithiophene (BT) or thieno[3,2‐b]thiophene (TT). PBTTPTI and PTTTPTI exhibit good solubility and strong interchain π–π interaction even in dilute solution. They possess deep HOMO levels (ca. ‐5.3 eV), partial crystallinity, and good hole mobilities. Blending with PC71BM, PBTTPTI and PTTTPTI give decent power conversion efficiencies (PCE) up to 6.83% and 5.86%, with outstanding fill factors (FF) of 74.3% and 71.3%, respectively.
Electron‐deficient heterocycle 1,3,4‐oxadiazole is first introduced to the 2‐position of thieno[3,4‐b]thiophene (TT) to construct a new building block 2‐(thieno[3,4‐b]thiophen‐2‐yl)‐5‐(alkylthio)‐1,3,4‐oxadiazole (TTSO) with alkylthio chain. The polymer PBDT–TTSO based on TTSO and benzodithiophene (BDT) exhibits a deep lying highest occupied molecular orbital (HOMO) energy level of −5.32 eV and low‐bandgap of 1.62 eV. The power conversion efficiency (PCE) of 5.86% is obtained with a relatively high VOC of 0.74 V, a JSC of 13.1 mA cm−2, and FF of 60.5%. Furthermore, as S atom in thioether can be oxidized easily, the optoelectronic properties of PBDT–TTSO treated with different oxidants are preliminary investigated. Interestingly, the oxidation products still maintain high PCE with reduction less than 30%. This work demonstrates a new method to regulate HOMO energy levels by introducing electron‐deficient aromatic heterocyclic moiety.
The chemical synthesis of a novel polyfuran, poly(2,3‐bis(hexylthio)‐[1,4]dithiino[2,3‐c]furan) ( PBDF ), substituted at the 2,3‐positions with an S‐alkylated dithiin unit, is reported. The new polymer has been characterized in terms of its electronic absorption, electrochemical, and thermal properties. Employment of the dithiin moiety provides intrinsic additional electroactivity, as well as a functional handle for substitution with alkyl groups, enhancing the processability of the polymer. The new polymer is compared with the closely related and well‐established literature compounds PEDOT and PEDTT as well‐studied, highly chalcogenated polythiophenes.
A rapid access to 2,2′‐bithiazole‐based copolymers has been developed on the basis of the sequential palladium‐catalyzed C H/C X and C H/C H coupling reactions. To assemble a “copolymer” through homopolymerization, a type of symmetric A‐B‐A‐type building block is designed as the monomer and prepared via the regioselective C5 H arylation of thiazole. A PdCl2/CuCl‐cocatalyzed oxidative C H/C H homopolymerization has been established to afford the 2,2′‐bithiazole‐based copolymers with high Mn (up to 69400). The current protocol features atom‐ and step‐economy and exhibits a potential in the highly efficient construction of conjugated copolymers.
The preparation of multifunctional polymers and block copolymers by a straightforward one‐pot reaction process that combines enzymatic transacylation with light‐controlled polymerization is described. Functional methacrylate monomers are synthesized by enzymatic transacylation and used in situ for light‐controlled polymerization, leading to multifunctional methacrylate‐based polymers with well‐defined microstructure.
Vinyl acetate is polymerized in the living way under the irradiation of blue light‐emitting diodes (LEDs) or sunlight without photocatalyst at ambient temperature. 2‐(Ethoxycarbonothioyl)sulfanyl propanoate is exclusively added and acts as initiator and chain transfer agent simultaneously in the current system. Poly(vinyl acetate) with well‐regulated molecular weight and narrow molecular weight distribution (Đ < 1.30) is synthesized. Near quantitative end group fidelity of polymer is demonstrated by nuclear magnetic resonance (NMR) and matrix‐assisteed laser desorption/ionization time‐of‐flight mass spectrometry (MALDI‐TOF MS).
Diblock metallopolymer polyelectrolytes containing the two redox‐robust cationic sandwich units [CoCp′Cp]+ and [FeCp′(η6‐C6Me6)]+ (Cp = η5‐C5H5; Cp′ = η5‐C5H4‐) as hexafluorophosphate ([PF6]−) salts are synthesized by ring‐opening metathesis polymerization using Grubbs' third generation catalyst. Their electrochemical properties show full chemical and electrochemical reversibilities allowing fine determination of the copolymer molecular weight using Bard–Anson's electrochemical method by cyclic voltammetry.
A novel one‐component type II polymeric photoinitiator, poly(vinyl alcohol)–thioxanthone (PVA–TX), is synthesized by a simple acetalization process and characterized. PVA–TX enables photopolymerization of methyl methacrylate and acrylamide in both organic and aqueous media. Photopolymerization proceeds even in the absence of a co‐initiator since PVA–TX possesses both chromophoric and hydrogen donating sites in the structure.
Surface‐initiated photo‐induced copper‐mediated radical polymerization is employed to graft a wide range of polyacrylate brushes from silicon substrates at extremely low catalyst concentrations. This is the first time that the controlled nature of the reported process is demonstrated via block copolymer formation and re‐initiation experiments. In addition to unmatched copper catalyst concentrations in the range of few ppb, film thicknesses up to almost 1 μm are achieved within only 1 h.
In this communication, a mild, efficient, and generalized polycondensation route is developed for poly(disulfide)s from commercially available monomers 2,2′‐dithiodipyridine and 1,6‐hexanedithiol. Using the stoichiometric imbalance between the two monomers, it is possible to produce telechelic poly(disulfide)s of predictable molecular weight with reactive pyridyl disulfide groups at both the terminals of the chain. The two terminal pyridyl disulfide groups can be quantitatively replaced by a functional thiol using selective thiol‐disulfide exchange and thus produces functional telechelic poly(disulfide)s, which can be used as a macroinitiator to initiate ring‐opening polymerization of a cyclic lactide monomer generating an ABA‐type triblock copolymer with degradable B block.
Diarylbutadiyne derivatives are ideal monomers for providing the π‐electron‐conjugated system of polydiacetylenes (PDAs). The geometrical parameters for diacetylene topochemical polymerization are known. However, control of the molecules under these parameters is yet to be addressed. This work shows that by simply tailoring diarylbutadiyne with amide side‐chain substituents, the arrangement of the substituents and the resulting hydrogen bond framework allows formation of π‐electron‐conjugated PDA.
The synthesis of tetracene‐ and pentacene‐annulated norbornadienes, formed through the Diels–Alder reaction of a dehydroacene with cyclopentadiene is reported. Ring‐opening metathesis polymerization (ROMP) leads to polymers that are investigated with respect to their physical, optical, and electronic properties by gel permeation chromatography (GPC), UV–vis spectroscopy, and cyclic voltammetry. The pentacene‐containing polymer P1 is successfully integrated into an organic field‐effect transistor (OFET); the tetracene‐containing polymer P2 is integrated into an organic light‐emitting diode (OLED).
A versatile one‐pot strategy for the preparation of reversibly cross‐linked polymer‐coated mesoporous silica nanoparticles (MSNs) via surface reversible addition–fragmentation chain transfer (RAFT) polymerization is presented for the first time in this paper. The less reactive monomer oligo(ethylene glycol) acrylate (OEGA) and the more reactive cross‐linker N,N′‐cystaminebismethacrylamide (CBMA) are chosen to be copolymerized on the external surfaces of RAFT agent‐functionalized MSNs to form the cross‐linked polymer shells. Owing to the reversible cleavage and restoration of disulfide bonds via reduction/oxidation reactions, the polymer shells can control the on/off switching of the nanopores and regulate the drug loading and release. The redox‐responsive release of doxorubicin (DOX) from this drug carrier is realized. The protein adsorption, in vitro cytotoxicity assays, and endocytosis studies demonstrate that this biocompatible vehicle is a potential candidate for delivering drugs. It is expected that this versatile grafting strategy may help fabricate satisfying MSN‐based drug delivery systems for clinical application.
Today's olefin metathesis catalysts show high reactivity, selectivity, and functional group tolerance and allow the design of new syntheses of precisely functionalized polymers. Here the synthesis of a new end‐capping reagent is investigated allowing the introduction of a highly reactive activated ester end‐group at the polymer chain end as well as its prefunctionalization to directly introduce functional moieties. The versatility of this new end‐capping reagent is demonstrated by utilizing it to synthesize a so‐called termimer (a monomer with termination capabilities). Copolymerization of a norbornene derivative with the termimer leads to hyperbranched ring‐opening metathesis polymerization polymers as proven by gel permeation chromatography and MALDI‐ToF‐(matrix‐assisted laser desorption/ionization time of flight) mass spectrometry.
A simple method is reported for the preparation of double‐helical structures through a series of achiral random and block copolymers poly(styrene‐co‐4‐vinylbenzyl triazolylmethyl methylthymine) (PS‐co‐PVBT) with various T units on the side chains through click reactions of poly(styrene‐co‐4‐vinylbenzyl azide) (PS‐co‐PVBN3) with propargyl thymine (PT) and also the synthesis of the A‐appended pyrene derivative (A‐Py) through click chemistry. This double‐helical structure is observed from achiral random‐coil polystyrene (PS) main chains, stabilized through the combination of multiple A–T hydrogen bonds, and π–π stacking between pyrene units and single‐walled carbon nanotubes (SWCNTs).
A new method for fabricating hydrogels with intricate control over hierarchical 3D porosity using microfiber porogens is presented. Melt electrospinning writing of poly(ε‐caprolactone) is used to create the sacrificial template leading to hierarchical structuring consisting of pores inside the denser poly(2‐oxazoline) hydrogel mesh. This versatile approach provides new opportunities to create well‐defined multilevel control over interconnected pores with diameters in the lower micrometer range inside hydrogels with potential applications as cell scaffolds with tunable diffusion and transport of, e.g., nutrients, growth factors or therapeutics.
Ethylene–propylene–methyl methacrylate (MMA) and ethylene–hexene–MMA A‐B‐C block copolymers with high molecular weight (>100 000) are synthesized using fluorenylamide‐ligated titanium complex activated by modified methylaluminoxane and 2,6‐di‐tert‐butyl‐4‐methylphenol for the first time. After diblock copolymerization of olefin is conducted completely, MMA is added and activated by aluminum Lewis acid to promote anionic polymerization. The length of polyolefin and poly (methyl methacrylate) (PMMA) is controllable precisely by the change of the additive amount of olefin and polymerization time, respectively. A soft amorphous polypropylene or polyhexene segment is located between two hard segments of semicrystalline polyethylene and glassy PMMA blocks.
