Polymer matrix effects on the nonlinear optical response of incorporated chromophore: new analytical models.

A new approach aimed at the modeling of the nonlinear optical (NLO) response of a dipole chromophore incorporated into a locally anisotropic, deformable, polarizable polymer matrix is suggested. The general continuum methodology is used with a specific cavity ansatz being employed; the cavity is chosen to be conformal to the characteristic ellipsoid of the generalized permittivity tensor of the polymer medium. The suggested ansatz allows the electrostatic boundary value problem to be solved analytically, and the local field experienced by the chromophore in the polymer electret to be found. Four analytically solvable models, which correspond to two singular and two nonsingular models, are considered; in two of them the chromophore is characterized by singular dipole and quadrupole moments; the other two use the approximation of the electric moment of the chromophore with that of the polarized ellipsoid. The relation between the macroscopic polymer properties and the microscopic characteristics of the NLO chromophore is established. The compliance of the obtained formulas for the local field with those of the classical Onsager approach is analyzed, and their specific features are considered.     

Synthesis, manipulation and conductivity of supramolecular polymer nanowires

The synthesis of supramolecular conducting nanowires can be achieved by using DNA and pyrrole. Oxidation of pyrrole in DNA-containing solutions yields a material that contains both the cationic polypyrrole (PPy) and the anionic DNA polymers. Intimate interaction of the two polymer chains in the self-assembled nanowires is indicated by FTIR spectroscopy. AFM imaging shows individual nanowires to be continuous, approximately 5 nm high and conformationally flexible. This feature allows them to be aligned by molecular combing in a similar manner to bare DNA and provides a convenient method for fabricating a simple electrical device by stretching DNA/PPy strands across an electrode gap. Current-voltage measurements confirm that the nanowires are conducting, with values typical for a polypyrrole-based material. In contrast to polymerisation of pyrrole on a DNA template in bulk solution, attempts to form similar wires by polymerisation at surface-immobilised DNA do not give a continuous coverage; instead, a beads-on-a-string appearance is observed suggesting that immobilisation inhibits the assembly process.     

Concise Multigram‐Scale Synthesis of Push–Pull Tricyanofuran‐Based Hemicyanines with Giant Second‐Order Nonlinearity: An Alternative for Electro‐optic Materials

Highly stable and highly soluble push–pull heptamethine hemicyanines based on the tricyanofuran electron‐accepting group can be prepared on a 15 g scale. The compounds display giant second‐order nonlinear figure of merit, μβ of up to 31 000×10^?48 esu, and lead to a poled material with a second‐order nonlinear response, r₃₃ of 90 pm V^?1 at 1.06 μm     

Optical characterization of pristine poly(3‐hexyl thiophene) films

We describe a comprehensive model for the optical properties of pristine films of poly‐(3‐hexylthiophene) (P3HT). The presented model is anisotropic with the optical axis normal to the substrate plane, which is consistent with previous x‐ray diffraction studies that show preferential edge‐on packing of the polymer chains on the substrate. Peak locations and spacings are defined using a Huang‐Rhys vibronic progression consistent with known phonon energies. We demonstrate that the model fits variable‐angle spectroscopic ellipsometry and normal‐incidence transmission data well, and accurately predicts angle‐ and polarization‐dependent transmission and reflection data. The spectral features of the optical constants used in the model are in excellent agreement with published spectroscopic data on P3HT. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010     

Polyamidoimides with side chromophoric groups

A new method was elaborated for the introduction of chromophores into the side chains of polymers by esterification of polyamidoimides containing side carboxy groups with glycidyl ethers of dyes, 4-(4-nitrophenylazo)phenol and 4-(6-nitrobenzothiazol-2-ylazo)phenol. The optimum modification conditions were found that made it possible to esterify 15, 30, 50, and 90% of the carboxy groups. The synthesized polymers possess valuable physicomechanical properties (E = 2.8–3.3 GPa, σ_u = 69–90 MPa, ε_u = 38–77%) and glass transition temperatures of 115–125 °C, depending on the degree of esterification. After chromophore orientation in the corona discharge, all the polymers demonstrate nonlinear optical properties of the second order. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1438–1444, June, 2005.     

Effect of different reaction parameters on the conductivity and dielectric properties of polyaniline synthesized electrochemically and modeling of conductivity against reaction parameters through regression analysis

The polyaniline (PAni) is prepared electrochemically from an aqueous solution of aniline and HCl in a single compartment electrochemical cell. Different PAni samples obtained by varying monomer concentration, acid concentration, applied potential, reaction time, and reaction temperature are subjected to conductivity and dielectric tests. The degree of crystallinity, d‐spacing, interchain separation, and crystallite size are determined form X‐ray analysis, the oxidation state is determined from infrared spectroscopy (FTIR) analysis, and the doping level is estimated from TGA analysis for all the PAni samples synthesized under different conditions. All these structural properties are correlated with electrical properties. The whole result reveals that all the aforementioned reaction parameters affect the structural properties, which in turn affect the electrical properties of PAni. The mathematical model correlations between conductivity and reaction parameters are established from the regression analysis for individual variables as well as for all the variables together. These relationships give the conductivity as an output when we input the value of reaction variables. The output obtained from the model relations found in well agreement with the experimental results under identical conditions. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2046–2059, 2007     

Novel conducting polymer poly[bis(phenylamino)disulfide]: Synthesis,characterization, and properties

A bis(phenylamino)disulfide was prepared through the reaction of S₂Cl₂ with aniline, and its configuration was confirmed with elemental analysis, Fourier transform infrared (FTIR), Fourier transform Raman (FT‐Raman), and ¹H NMR spectroscopy. A novel conducting polymer, poly[bis(phenylamino)disulfide] (PPAD), was synthesized from bis(phenylamino)disulfide by both chemical and electrochemical polymerization. The structure of this polymer, in which the side‐chain disulfide bonds were linked to the nitrogen atoms of the main‐chain polyaniline, was characterized with FTIR, FT‐Raman, gel permeation chromatography, electron spectroscopy, and X‐ray photoelectron spectroscopy. A four‐probe measurement revealed that the electrical conductivity of PPAD was 1.8 × 10^?2 to 2.1 × 10^?3 S cm^?1, depending on the doping agents and the pH of the medium for either chemical synthesis or electrochemical synthesis. The conductivity, molecular weight, and spectroscopic properties of the polymer, in comparison with those of polyaniline, showed decreases in the polaron delocalization, structural order, and doping level of the main chain because of the steric hindrance of side‐chain S? S bonds. The cyclic voltammograms of the polymer and the monomer showed that the redox reactions (doping/undoping processes) of the main chain (π‐conjugated system) occurred in almost the same potential range of ?0.3 to 0.3 V versus an Ag/AgCl (saturated KCl) electrode as that of thiol (thiolate anion)/disulfide of the side chain in PPAD; the bond cleavage (reduction) and formation (oxidation) reactions of the disulfide bond in the polymer became easier and more reversible than those of the monomer. These results suggested that this conducting organodisulfide polymer might be a candidate material for energy‐storage devices such as lithium secondary batteries, proton‐exchange batteries, and electrochemical capacitors. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2329–2339, 2004     

Conductivity enhancement in raw polypyrrole and polypyrrole nanoparticle dispersions

For certain commercial applications of polypyrrole (PPy), an enhancement of the electrical conductivity of the material is the key to industrial success. In this paper it will be shown that raw PPy with high conductivity (>150 S/cm) can be obtained in very good yield (>90%) by appropriate selection of both bi‐functional additives and reaction conditions which increase the oxidative polymerization rate of pyrrole. The presence of new active centers for the polymerization is demonstrated by UV measurements. In addition, raw PPy synthesized according to the improved method of synthesis shows good stability of the conductivity upon aging at high temperature (150°C) in air. Finally, new PPy dispersions are reported with an average particle size of 67 nm obtained by sonochemical synthesis that can be incorporated into conventional plastic paints for direct metallization of plastics. The conductivity of the new metallization paint developed was 0.4 S/cm with a PPy content of 10 wt%. Copyright © 2006 John Wiley & Sons, Ltd.     

Synthesis and tunable properties of oligoaniline‐functionalized polyamides

Electroactive polyamides containing dense oligoaniline functionalizations (PAs) were synthesized via oxidative coupling polymerization followed by postpolymerization functionalization, and exhibit excellent solubility, good thermal stability and reversible electroactivity. Interesting spectroscopic changes that occurred through chemical oxidation have been shown, which demonstrate the potential of PAs as an electrochromic material. As a result, the electrochromic behaviors of PAs were investigated in detail, exhibiting high contrast value, moderate switching time, and satisfactory coloration efficiency. Tunable conductive and dielectric properties have also been accomplished by varying the incorporation of oligoaniline segments. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3343–3349     

Synthesis and proton conductivity studies of polystyrene‐based triazole functional polymer membranes

In this study, poly(vinylbenzylchloride) (PVBC) was produced by free‐radical polymerization of 4‐vinylbenzylchloride, and then it was functionalized with 3‐amino‐1,2,4‐triazole (ATri) and 1H‐1,2,4‐triazole (Tri). The composition of the polymers was verified by elemental analysis, and the structure was characterized by Fourier transform infrared and ¹³C‐nuclear magnetic resonance spectra. PVBC was modified by ATri with 68% and Tri with 50% yield. The polymers were doped with trifluoromethanesulfonic acid (TA) at various molar ratios, X = 0.5, 1, 2, and 3 with respect to aminotriazole and triazole units. Proton transfer from TA to the triazole rings was proved with Fourier transform infrared spectroscopy. Thermogravimetric analysis showed that the samples are thermally stable up to approximately 200 °C. Differential scanning calorimetry results illustrated the homogeneity of the materials. Under anhydrous conditions, PVBCATri3TA and PVBCTri3TA showed highest proton conductivity of 0.086 and 0.042 S/cm, respectively. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Templateless assembly of molecularly aligned conductive polymer nanowires: a new approach for oriented nanostructures

Although oriented carbon nanotubes, oriented nanowires of metals, semiconductors and oxides have attracted wide attention, there have been few reports on oriented polymer nanostructures such as nanowires. In this paper we report the assembly of large arrays of oriented nanowires containing molecularly aligned conducting polymers (polyaniline) without using a porous membrane template to support the polymer. The uniform oriented nanowires were prepared through controlled nucleation and growth during a stepwise electrochemical deposition process in which a large number of nuclei were first deposited on the substrate using a large current density. After the initial nucleation, the current density was reduced stepwise in order to grow the oriented nanowires from the nucleation sites created in the first step. The usefulness of these new polymer structures is demonstrated with a chemical sensor device for H(2)O(2), the detection of which is widely investigated for biosensors. Finally, we demonstrated that controlled nucleation and growth is a general approach and has potential for growing oriented nanostructures of other materials.     

Conductivity of Poly(pyrrole)‐Poly(styrene sulfonate) Core–Shell Nanoparticles

The dielectric properties of poly(styrene) nanoparticles decorated at their surfaces with poly(styrene sulfonate) [PSS] brushes and subsequently loaded with polypyrrole (PPy) were studied. These film‐forming materials which may serve as hole‐injection layers in organic light‐emitting diodes, exhibit a core–shell‐type morphology with a core of electrically insulating poly(styrene) and a shell consisting of a corona of PSS chains which form the matrix in which the electrically conducting complex of PPy and PSS is embedded. This conducting complex exists in form of domains of nanoscale dimensions. Thin compressed pellets of these nanoparticles were studied using mainly impedance spectroscopy. Measurements were carried out in the temperature range between 123 and 453 K and frequency range from 10^?1 to 10⁶ Hz. While earlier studies were centered around the effect of polypyrrole volume fraction on the conductivity films and pellets composed of these nanoparticles, the present study reveals in which way the conductivity can be modified by exchange of the mobile inorganic counter ions of PSS. Besides the free‐acid form (H⁺), the Li⁺‐, Na⁺‐ and Cs⁺‐salts of PSS were investigated. The PPy volume fraction was the same for all PPy/PSS core–shell nanoparticles. The distance for phonon‐assisted hopping between next‐neighbor polypyrrolium chains is influenced by the presence of these inorganic cations. For all samples containing PPy, a transition from insulating to conducting behavior in the range of 300‐350 K was found. Using the fluctuation‐induced tunneling model, the average tunneling distance, as well as the potential energy barrier separating neighboring conducting grains was estimated. Finally, a detailed analysis of the dielectric spectra suggests the localization length of the charge carriers to be about 0.33 nm.     

Secondary relaxations and electrical conductivity in hyperbranched polyester amides

Broadband dielectric spectroscopy is used to investigate molecular dynamics and charge transport in three hyperbranched polyester amides with hydroxyl, phenyl, and stearate terminal groups. At higher temperatures, the dielectric spectra are interpreted in terms of hopping conduction in a spatially randomly varying energy landscape, whereas two secondary dipolar relaxations attributed to librations of the terminal and amide groups dominate the low temperature regime. Despite a shift of more than 3 decades in the dc conductivity upon variation of the end groups, the Barton–Nakajima–Namikawa relation is shown to hold. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1651–1657, 2010     

High‐Conductivity Two‐Dimensional Polyaniline Nanosheets Developed on Ice Surfaces

A new method to develop two‐dimensional PANI nanosheets using ice as a removable hard template is presented. Distinctly high current flows of 5.5 mA at 1 V and a high electrical conductivity of 35 S cm^?1 were obtained for the polyaniline (PANI) nanosheets, which marked a significant improvement from previously values on other PANIs reported over the past decades. These improved electrical properties of ice‐templated PANI nanosheets were attributed to the long‐range ordered edge‐on π‐stacking of the quinoid ring, ascribed to the ice surface‐assisted vertical growth of PANI. The unprecedented advantages of the ice‐templated PANI nanosheets are two‐fold. First, the PANI nanosheet can be easily transferred onto various types of substrates via float‐off from the ice surfaces. Second, PANI can be patterned into any shape using predetermined masks, and this is expected to facilitate the eventual convenient and inexpensive application of conducting polymers in versatile electronic device forms.     

Second‐Order Nonlinear Optical Activity of Dipolar Chromophores Based on Pyrrole‐Hydrazono Donor Moieties

Donor1+donor2→acceptor : The second‐order NLO molecular properties of a class of dipolar chromophores that incorporate the following design elements are investigated: 1) a substituted hydrazono moiety as a strong donor; 2) a pyrrole ring as an auxiliary donor; 3) strong acceptor groups (see figure). Their first hyperpolarisabilities show good promise for use in electro‐optical devices.

     

Macroscopic order and electro-optic response of dipolar chromophore-polymer materials.

This Minireview considers the key factors that govern the organization of macroscopic polarization in nonlinear optical systems obtained by electric poling of organic dipolar chromophores dissolved in polymer matrices. The macroscopic electric polarization depends on the thermodynamic state of the dipole system. The dependence of the paraelectric and antiferroelectric states of dipolar chromophores on the chromophore concentration and the strength of the poling field is discussed. Phase transitions between the para- and antiferroelectric states are investigated within the limits of the Ising and isotropic models for the chromophore dipoles and are considered for varying chromophore concentration, poling field strength, and macroscopic shape of the sample used for poling. The macroscopic polarization and electro-optic coefficient of the material change drastically upon phase transition. The theories are compared with the experimental data on the electro-optic coefficient dependence on the chromophore concentration. The isotropic dipole model shows excellent agreement with experiment for the chromophore systems most commonly used in nonlinear optics.