Synthesis and electrochemical characterization of fluorene and benzimidazole containing novel conjugated polymers: Effect of alkyl chain length on electrochemical properties

The synthesis and characterization of two donor acceptor type conjugated polymers were investigated. Electrochemical properties were examined by cyclic voltammetry, spectroelectrochemistry and kinetic studies. The increase in the alkyl chain length attached to the fluorene unit was investigated in terms of electrochemical properties. The synthesis was carried out via Stille coupling of 4,7-dibromo-4′-(tert-butyl)spiro[benzo[d]imidazole-2,1′ cyclohexane] and 2,5-bis(tributylstannyl)thiophene with 9,9-dihexyl-9H fluorine (P1) and 9,9-didodecyl-9H fluorene (P2) respectively. Both polymers were neutral state green polymers. They had optical band gaps of 1.55 and 1.47 eV respectively. Increasing the chain length resulted in an increase in solubility and processibility of the polymer. Polymers are multichromic, revealing colors from neutral state green to doped state blue.     

Synthesis and characterization of a new soluble conducting polymer and its electrochromic device

A mixture of isomers 2,5-di(4-methyl-thiophen-2-yl)-1-(4-nitrophenyl)-1H-pyrrole, 2-(4-methyl-thiophen-2-yl)-5-(3-methyl-thiophen-2-yl)-1-(4-nitrophenyl)-1H-pyrrole and 2,5-di(3-methyl-thiophen-2-yl)-1-(4-nitrophenyl)-1H-pyrrole (Me-SNS(NO₂)) were synthesized. Resulting monomers were polymerized chemically, producing soluble polymers in common organic solvents. The average molecular weight has been determined by gel permeation chromatography (GPC) as Mn=5.6×10³ for the chemically synthesized polymer. The monomers were also electrochemically polymerized in the presence of LiClO₄, NaClO₄ (1:1) as the supporting electrolyte in acetonitrile solvent. Resulting polymers were characterized via CV, FTIR, NMR, SEM and UV–Vis spectroscopy. Spectroelectrochemistry analysis of polymer revealed Π–Π^* transition below 300 nm, with an electronic band gap of 2.18 ev. Switching ability of the polymer was evaluated by kinetic study measuring percent transmittance (%T) at the maximum contrast point, indicating that poly(Me-SNS(NO₂)) is a suitable material for electrochromic devices.     

Thiadiazoloquinoxaline and benzodithiophene bearing polymers for electrochromic and organic photovoltaic applications

Abstract

Two novel thiadiazoloquinoxaline and benzodithiophene (BDT) bearing copolymers were designed and synthesized. Different BDT units (alkoxy and thiophene substituted) were used as donor materials and the effect of alkoxy and thiophene substitution on the electrochemical, spectroelectrochemical and photovoltaic properties were investigated. Both polymers exhibited low oxidation potentials at around 0.90 V and low optical band gaps at around 1.00?eV due to the insertion of electron poor thiadiazoloquinoxaline unit into the polymer backbone. Both P1 (poly-6,7-bis(3,4-bis(decyloxy)phenyl)-4-(4,8-bis(nonan-3-yloxy)benzo[1,2-b:4,5-b']dithiophen-2-yl)-[1, 2, 5]thiadiazolo[3,4-g]quinoxaline) and P2 (poly- 4-(4,8-bis(5-(nonan-3-yl)thiophen-2-yl)benzo[1,2-b:4,5-b']dithiophen-2-yl)-6,7-bis(3,4-bis(decyloxy)phenyl)-[1, 2, 5]thiadiazolo[3,4-g]quinoxaline) exhibited multichromic behavior with different tones of greenish yellow and gray in the neutral and fully oxidized states, respectively. In addition, both polymers revealed very high optical contrasts (～87%) in the NIR region which make these promising polymers good candidates for NIR applications. Finally, in order to explore the organic photovoltaic performances, P1 and P2 were mixed with PC₇₁BM in the active layer of organic solar cells (OSCs) by conventional device structure. As a result P1 and P2 based devices revealed power conversion efficiencies (PCEs) of 0.33% and 0.60% respectively. However, the additive treatment enhanced PCE from 0.49 to 0.73% for P2 based devices.     

Molecularly imprinted polymer film interfaced with Surface Acoustic Wave technology as a sensing platform for label-free protein detection

Molecularly imprinted polymer (MIP)-based synthetic receptors integrated with Surface Acoustic Wave (SAW) sensing platform were applied for the first time for label-free protein detection. The ultrathin polymeric films with surface imprints of immunoglobulin G (IgG-MIP) were fabricated onto the multiplexed SAW chips using an electrosynthesis approach. The films were characterized by analyzing the binding kinetics recorded by SAW system. It was revealed that the capability of IgG-MIP to specifically recognize the target protein was greatly influenced by the polymer film thickness that could be easily optimized by the amount of the electrical charge consumed during the electrodeposition. The thickness-optimized IgG-MIPs demonstrated imprinting factors towards IgG in the range of 2.8–4, while their recognition efficiencies were about 4 and 10 times lower toward the interfering proteins, IgA and HSA, respectively. Additionally, IgG-MIP preserved its capability to recognize selectively the template after up to four regeneration cycles. The presented approach of the facile integration of the protein-MIP sensing layer with SAW technology allowed observing the real-time binding events of the target protein at relevant sensitivity levels and can be potentially suitable for cost effective fabrication of a biosensor for analysis of biological samples in multiplexed manner.     

Synthesis and properties of acceptor-donor-acceptor molecules based on oligothiophenes with tunable and low band gap

A series of acceptor-donor-acceptor molecules (DCN3T, DCN5T and DCN7T) based on oligothiophenes with low band gap are synthesized. The UV-vis absorption spectra of solution show that the introduction of electron-accepting groups results in a shift of the absorption onset towards longer wavelengths. Moreover, the optical spectra of their films show a large bathochromic shift and broadening of the bands with respect to the spectra in solution. The optical band gaps of film of these A-D-A molecules are 1.90, 1.74 and 1.68 eV, respectively. Cyclic voltammetry shows that all these compounds present a reversible first oxidation process whose potential decreases with the lengthening of oligothiophene cores. Electrochemical band gaps are 2.14, 1.88 and 1.71 eV, respectively.     

Electrochemical properties of PP membranes with plasma polymer coatings of acrylic acid

Commercial polypropylene (PP) membranes were modified by plasma polymerization coating of acrylic acid, in combination with oxygen flow or oxygen plasma etching. First, conditions for plasma polymerization coating were optimized in terms of the chemical resistance of the coatings and their ion exchange capacity as a function of plasma power, internal pressure and treatment time. Next, the plasma polymerization coating of acrylic acid was combined with oxygen flow or oxygen plasma etching, and their conditions were also optimized by measuring the ion exchange capacity. Finally, the modified membranes were subjected to electrical resistance and transport number measurements and characterized by -step, FT-IR/ATR and SEM. Among the modification methods, oxygen plasma etching followed by the plasma polymerization coating of acrylic acid provided the best electrochemical properties with 1.75 meq/g (IEC) and 112 Ω cm² (ER), 0.88 (TN).     

Effects of polymer network on electrically induced reflection band broadening of cholesteric liquid crystals

The reflection band of polymer stabilized cholesteric liquid crystals with negative dielectric anisotropy can be broadened by DC electric fields, which was ascribed to the pitch gradient caused by the motion of the structural chirality, that is, the polymer network. They systematically varied the mixture components, such as the photo‐initiator concentration, the monomer functionality, and the chiral dopant, to explore their influences on the reflection band broadening behavior. They learned how to control the polymer network morphology and ion density, which in turn determined the reflection bandwidth. By optimizing the mixture, they have greatly enhanced the broadening effect and achieved large bandwidth at low voltages. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 835–846     

Thienopyrazine or dithiadiazatrindene containing low band gap conjugated polymers for polymer solar cells

Four new low-band-gap alternating copolymers （P-1, P-2, P-3 and P-4） based on electron-rich benzodithiophene and newly developed electron-deficient units, thienopyrazine or dithiadiazatrindene derivatives, were synthesized by Stille polycondensation. All polymers exhibit good solubility in common organic solvents and a broad absorption band in the visible to near-infrared regions. The film optical band gaps of the polymers are in the range of 1.28-2.07 eV and the highest occupied molecular orbital （HOMO） energy levels are in the range of-4.99 eV to -5.28 eV. Bulk heterojunction polymer solar cells （PSCs） of the polymers were fabricated with phenyl-C61-butyric acid methyl ester （PC61BM） as acceptor material, and a power conversion efficiency of 0.80% was realized with P-1 as donor material.     

Supramolecular design of a porphyrin-[60]fullerene photocurrent generation system on a DNA scaffold fabricated by a conjugate polymer film

DNA which binds monocationic [60]fullerene (1) and tetracationic porphyrin (TMPyP) was readily fabricated by electrochemical oxidative polymerization of 3.4-ethylenedioxythiophene (EDOT) and the resultant poly(EDOT) composite was deposited on an ITO electrode as a stable thin film. Spectral and CV analyses established that one 1 and one TMPyP are bound per 57 nucleobase units, that is, every three pitches of DNA. Photoirradiation of this 1/TMPyP/DNA-poly(EDOT) film generated a photocurrent in 3.8% quantum yield, which was much higher than those obtained from 1/DNA and TMPyP/DNA systems. One can conclude, therefore that the photoexcited energy of TMPyP is transferred to 1, which is collected by the electron-conducting poly(EDOT) film. The present paper shows that DNA is useful as a scaffold to arrange redox-active couples in a one-dimensional matrix.     

Electrosynthesis and characterization of aminomethyl functionalized PEDOT with electrochromic property

We herein report the electrosynthesis of an aminomethyl functionalized poly(3,4-ethylenedioxythiophene)(PEDOT) derivative, poly(2'-aminomethyl-3,4-ethylenedioxythiophene)(PEDOT-Me NH2), in CH2Cl2-Bu4NPF6(0.1 mol·L-1) system containing 2% boron trifluoride diethyl etherate(BFEE). The electrochemical behavior, structure characterization, thermal properties and surface morphology of this novel polymer were systematically investigated by cyclic voltammetry(CV), Fourier-transform infrared spectroscopy(FTIR), thermogravimetry(TG) and scanning electron microscopy(SEM), respectively. Electrochemistry results demonstrated that PEDOT-Me NH2 film displayed good redox properties and high electrochemical stability. Besides, PEDOT-Me NH2 films exhibited the electrochromic nature with obvious color changing from purple in the reduced form to blue upon oxidation. By further investigation, kinetic studies revealed that PEDOT-Me NH2 film had decent contrast ratio(41.8%), favorable coloration efficiency(152.1 cm2·C-1), low switching voltages and moderate response time(2.4 s). Satisfactory results implied that the obtained PEDOT-Me NH2 film is a promising optoelectronic material and holds promise for electrochromic devices and display applications.     

Potential switching of optical properties in polymer electrolytes

The electric field dependence of the optical properties of a series of anion-conducting polymer electrolytes at an ITO–electrolyte interface was investigated. A change in reflectance and refractive index of polymer electrolytes [poly(ethyl methacrylate)]₁₈(Bu₃SnX)₃Bu₄NX where X = Cl, Br, and SCN was observed. This was ascribed to anion accumulation/depletion in the interfacial region. Shorter response times were observed for electrolytes with higher conductivities, illustrating the interrelationship between these two phenomena. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2057–2062, 1997     

Monitoring morphological and optical properties on hybrid porous polymer films

This work focuses on an optical and morphological comparative study of hybrid functional polymer porous films on glass substrates using the spin coating technique. The covering of these membranes, by a predeposited Zn²⁺ seed layer, was done applying the dip casting technique, which allows the synthesis of a large area and the control of the orientation of ZnO nanoparticles. It was possible to observe changes on the optical properties and surface morphology, which were attributed to both the spatial structure of the macromolecule and their interaction with the inorganic nanoparticles. It was also clear that hybrid porous matrices exhibit a blueshift with decreasing particle size.     

Monitoring the deposition process of metal-doped polymer films using optical emission spectroscopy

Simultaneous plasma polymerization of halocarbons (CF₄ and C₂F₃Cl) and sputtering of metals (Au and Al) or cosputtering [Au + polytetrafluoroethylene (PTFE, Teflon)] have been performed by means of an RF (20 MHz) glow discharge excited by a planar magnetron. The optical emission spectroscopy (OES) has been used for monitoring the deposition process of metal-doped polymer films. The light emission intensity ratios of the relevant species in the plasma volume are given in connection with the characteristics of the films prepared.     

Anti-biofouling properties of an amphoteric polymer brush constructed on a glass substrate

An amphoteric copolymer brush of methacrylic acid (MA) and 2-(dimethylamino)ethyl methacrylate (DMAEMA) was prepared by reversible addition-fragmentation chain-transfer (RAFT) polymerization using both a free chain transfer agent (n-butylsulfanylthiocarbonylsulfanyl-2-methyl propionic acid) and a radical initiator (4,4'-azobis(4-cyanopentanoic acid)) covalently fixed to a glass substrate. An aqueous solution of the copolymer, Poly(MA-r-DMAEMA), which was simultaneously obtained in liquid phase, had a sufficiently small polydispersity in its molecular weight. The copolymer brush showed effective suppression of non-specific adsorption of bovine serum albumin and egg white lysozyme to the brush. In contrast, both negatively charged PolyMA and positively charged PolyDMAEMA brushes significantly adsorbed the proteins irrespective of their net charges. Upon ion beam irradiation, furthermore, a hollow space with a designed shape could be made on the glass substrate, and both HEK293 and HepG2 cells non-specifically adhered to the space, forming aggregates, while no adhesion to the non-treated area on the brush was observed. These results suggest that the amphoteric polymer brushes will be useful materials for biomedical applications.     

Interpenetrating polymer networks with stable second order nonlinear optical properties

Interpenetrating polymer networks (IPNs) based on polyurethane and polyacrylate-containing 4-(4'-nitrophenylazo) aniline chromophore groups were synthesized and characterized by infrared spectra, gel content and differential scanning calorimetry. Thin, transparent films of the IPNs were prepared by spin-coating, followed by thermal curing and corona poling. The poled IPN film shows very good optical properties and exhibits only one glass transition temperature. The second-order nonlinear optical (NLO) properties of the poled film were studied by visible light absorbance measurement according to one-dimensional rigid oriented gas model. The second-order nonlinear optical polarizability can reach 10^-7 e.s.u. The poled IPN film of defined composition showed a good temporal stability of NLO properties at 120°C for more than 160 hr.     

Synthesis,characterization, and application of metal-free sulfonamide-vitamin C adduct to improve the optical properties of PVA polymer

Improving optical properties is an important topic in the field of polymer science. In this research, a novel, metal-free, and inexpensive vitamin C sulfonamide adduct has been developed to enhance the optical behaviors of polyvinyl alcohol (PVA). Initially, the vitamin C adduct has been fabricated through atom economic reaction and then characterized using several spectroscopic techniques, including ¹H NMR, ¹³C NMR, DEPT-135, Fourier transform infrared spectroscopy (FTIR), and X-ray diffraction (XRD). Accordingly, a dramatic chemical alteration in ascorbic acid structure has been confirmed and led to enhancing chemical interactions with the host polymer. The ascorbic acid adduct has been doped into PVA to prepare a flexible film of polymer composites with potential optical behaviors. The identity of composite film has specified from FTIR, XRD, and UV–vis spectroscopy. The XRD pattern of the hybrid polymer has revealed a remarkable boost in its amorphous structure compared to the PVA host. The FTIR data of both matrix PVA and its composites reveal the potent chemical interactions of functional groups within the hybrid PVA. The main optical information of synthesized hybrid film was obtained from the UV–vis spectra. The refractive index (n) and dielectric loss (ε_i) values are elevated notably, whereas the optical band gap energy (E_g) declined from 6.3 to 3.6 eV. The direct electronic transition between the valence band (VB) and conduction band (CB) was determined by implementing Tauc’s model. These preliminary results suggest that the fabricated flexible composite will have an excellent opportunity to use in the manufacturing optical devices.     

Compositional effect of PVdF-PEMA blend gel polymer electrolytes for lithium polymer batteries

Owing to their improved mechanical properties and good polymer miscibility, the blend gel polymer electrolytes of poly (vinylidene fluoride) (PVdF)-poly(ethyl methacrylate) (PEMA) have been prepared using solvent casting technique and characterized for their electrochemical performances. The electrolyte shows a maximum ionic conductivity of 1.5 × 10⁻⁴ S cm⁻¹ at 301 K for the 90:10 blend ratio of PVdF:PEMA system with good transport property. The ionic conductivity is enhanced, in accompany with improved microstructural homogeneity, at low PEMA contents, while the decreased conductivity at high contents has been attributed to increasing crystalline PEMA domains. With the optimum PVdF:PEMA ratio, the complex system was found to facile reasonable ionic transference number and exhibit superior interfacial stability with Li electrode.     

Direct arylation synthesis of thienoisoindigo‐based low‐band‐gap polymer from asymmetric donor–acceptor monomer

Thienoisoindigo (TIG) moiety has been paid numerous attentions as an excellent acceptor building block in low‐band‐gap polymers. Herein, a new TIG‐dithiophene alternating copolymer (PTIG2T) was successfully synthesized from an asymmetric TIG‐based donor–acceptor (D‐A) monomer via the self‐condensation‐type direct arylation polymerization. PTIG2T exhibited the light absorption over 1000 nm owing to the intramolecular charge transfer in the thin film state, which corresponded to an optical band gap of 1.24 eV. The HOMO and LUMO levels of PTIG2T were determined to be −5.08 and −3.60 eV, respectively. Furthermore, the organic photovoltaic (OPV) with a PTIG2T/PC₆₁BM active layer achieved a power conversion efficiency (PCE) of 3.19%, which is one of the highest PEC achieved by OPVs with TIG‐based materials. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 430–436