Influences of the electron donor groups on the properties of thiophene-(N-aryl)pyrrole-thiophene-based organic sensitizers

In this study, 1-(2,6-diisopropylphenyl)-2,5-di(2-thienyl)pyrrole-based metal-free organic dyes containing three different non planar electron donor groups such as methoxy or hexyloxy substituted triphenylamine and difluorenephenylamine were prepared in order to see the effect of electron donor groups on the opto-electrical properties and applied in dye-sensitized solar cells (DSSC). All three dyes showed broad absorption band in visible part of the solar spectrum (∼300 nm–600 nm). The dye (TPTDYE-3) containing sterically less hindered methoxy substituted triphenylamine was found to show relatively red shifted absorption compared to that of the dye (TPTDYE-4) containing hexyloxy substituted triphenylamine or the dye (TPTDYE-5) containing difluorenephenylamine. The optical band gaps of the three dyes were calculated to be 2.19 eV, 2.22 eV and 2.24 eV, respectively, and the highest occupied molecular orbital (HOMO) energy levels of the three dyes were found to be located at 0.65 V, 0.68 V and 0.75 V, respectively. The DSSC performance of each dye was investigated with and without coadsorbent. The maximum solar to electrical energy conversion efficiencies (η) of the DSSCs made from only sensitizer were 4.18%, 5.28% and 5.42% while those of the DSSCs made from sensitizer with coadsorbent were 5.47%, 5.58% and 5.63%, respectively.     

Spectroscopic and dielectric studies of meso-tetrakis(p-sulfonatophenyl) porphyrin doped hybrid borate glasses

Hybrid borate glasses containing different concentrations of meso-tetrakis(p-sulfonatophenyl) porphyrin sodium salt (TPPS₄) were prepared. The obtained glass samples were found to be transparent and homogeneous. Formation of TPPS₄-J-aggregates in borate glass was investigated by means of optical absorption, steady state and time resolved fluorescence spectroscopy. The hybrid glasses exhibit a strong S₂→S₀ emission at ∼473 nm and J-aggregates show emission at ∼733 nm. Time resolved fluorescence show two exponential decay with lifetime of τ₁ = 65 ± 10 ps (∼80%) and τ₂ = 3.87 ± 0.1 ns (∼20%) respectively. Dielectric properties such as dielectric constant (?′), dielectric loss (tan δ) and ac conductivity (σ_ac) over a range of frequency and temperature of these glasses were studied. The ac conductivity was found to be proportional to ω^s (where s < 1). The observed change in dielectric parameters due to different concentrations of TPPS₄ has been analyzed in light of different polarization mechanisms.     

Synthesis and characterization of efficient orange-red emitting poly(p-phenylenevinylene) derivatives with 1,3,4-oxadiazole unit

A series of the statistical copolymers of tetradecyloxy-3,5-bis-{2-(4-bromo-phenyl)-[1,3,4]oxadiazole}-benzene (4), 1,4-didecyloxy-2,5-diiodobenzene (5) and 1,4-dodecyloxy-2,5-divinylbenzene (6), for efficient light emitting diode were synthesized. As the feed ratio of compound 4 decreased, the absorption band at 320–360 nm decreased in the UV–vis spectra. In addition, as the composition of compound 4 decreased, the absorption intensity ratio at 1541 cm⁻¹ decreased in the FT-IR spectra. The photoluminescence and electroluminescence emission color of P showed green-yellow color (λ_max = 552 nm). However, the maximum wavelength of photoluminescence and electroluminescence of P1 and P2 were 581 and 583 nm, respectively, which were dramatically red-shifted than that of P. Moreover, these values were almost the same as the values of P3 (580 nm). It is concluded that the energy transfer from high energy oxadiazole segments to low energy alkoxy-PPV segments occurred completely. The efficiency of ITO/P2/Al was 0.0181%, which is the best efficiency among the device based on the copolymers. This is presumably due to that P2 has the best balanced hole- and electron-injection/transporting properties among the copolymers.     

Electrodeposition of pyrrole and 3-(4-tert-butylphenyl)thiophene copolymer for supercapacitor applications

The electropolymerization of pyrrole (Py), 3-(4-tert-butylphenyl)thiophene (TPT) monomer or the mixed Py and TPT monomers on stainless steel mesh substrate were performed in 1 M LiClO₄/acetonitrile solution. A much lower potential of 0.75 V was required for the co-electropolymerization of Py and TPT, in sharp contrast to that of 1.20 V for poly(3-(4-tert-butylphenyl)thiophene) (PTPT) formation. The resultant homopolymers and copolymer were characterized with FESEM and FTIR, and assembled into supercapacitors to investigate their electrochemical performances. The copolymer electrode delivered the highest specific capacitance of 291 F g⁻¹ at a scan rate of 5 mV s⁻¹, in comparison with that of 216 and 26 F g⁻¹ for PPy and PTPT, respectively. This copolymer also exhibited a greatly improved cycling stability – only 9% of capacitance decrease was observed after 1000 charging–discharging cycles at a current density of 5 A g⁻¹, while the capacitance losses for PPy and PTPT were 16% and 60%, respectively.     

Synthesis of highly conductive poly(3,4-ethylenedioxythiophene) fiber by simple chemical polymerization

Poly(3,4-ethylenedioxythiophene) (PEDOT) fiber was chemically synthesized by the polymerization of 2,5-dihalo-3,4-ethylenedioxythiophene in the presence of BF₃ without a template. The resulting conductive PEDOT fiber exhibited conductivity in the range of 150–250 S/cm (pressed powder pellet). The thermal stability of PEDOT was also improved and UV-spectroscopy analysis of a film exhibited a strong absorption band at 460 nm. The well-defined needle-shaped fibers of PEDOT were examined by SEM, and the average length and diameter of the fibers were 10 and 0.4 μm, respectively.     

A new donor–acceptor type conjugative poly{2-[4-(1-cyanoethenyl)phenyl]-3-(3,4-didodecyloxythiophen-2-yl)prop-2-enenitrile}: Synthesis and NLO studies

This research article describes a technique to synthesize a new donor–acceptor type conjugated polymer carrying cyanophenylenevinylene and 3,4-didodecyloxy thiophene moieties, as an effective optical limiting material. It also includes the evaluation of its linear and nonlinear optical properties and electrochemical studies. The new polymer, viz., poly{2-[4-(1-cyanoethenyl)phenyl]-3-(3,4-didodecyloxythiophen-2-yl)prop-2-enenitrile} (P1) has been synthesized starting from 2,2′-sulfanediyldiacetic acid and diethyl ethanedioate through multistep reactions. In the final step, the polymerization was brought about by Knovenagel condensation. The newly synthesized intermediate, monomer and the polymer (P1) have been characterized by different spectroscopic techniques followed by elemental analysis. Its optical and electrochemical properties are investigated by UV–vis, fluorescence spectroscopy and cyclic voltammetric studies, respectively. The red colored polymer has a well defined structure, good thermal stability and a band gap of 1.78 eV. It emits green fluorescence both in solution and in film state. The third-order nonlinear optical property (NLO) of the polymer was studied by the Z-scan technique. The measurements were performed at 532 nm with 5 ns laser pulses using samples in solution form. An absorptive nonlinearity of the optical limiting type was found in this polymer, which is due to the combined action of saturable absorption and excited state absorption processes. These studies revealed that polymer P1 is a promising material for optical limiting applications.     

Synthesis and third-order nonlinear optical studies of a novel four-coordinated organoboron derivative and a bidentate ligand: The effect of the N → B coordinative bond

The third-order nonlinear optical characterization of a new boronate (2) derived from 4-dimethylaminocinnamaldehyde was performed by third-harmonic generation (THG) at the infrared wavelength of 1550 nm. Compound 2 was prepared from the reaction of diphenylboronic acid and the bidentate ligand (1) and characterization was made through UV, IR, ¹H, ¹¹B, and ¹³C NMR and X-ray diffraction. The THG experiments showed that the N → B coordinative bond in 2 enhanced the second molecular hyperpolarizability of the type γ⁽³⁾(−3ω, ω, ω, ω) by a factor of three with respect to the value exhibited by the ligand 1. On the other hand, Z-scan studies at 800 nm (femtosecond (fs) pulses) also showed that such coordinative bond increased the nonlinear absorption (two-photon absorption (TPA)) in 2 with respect to 1. These studies demonstrate that the N → B coordinative bond facilitates the polarization of the electronic π-system, a situation that optimizes the third-order NLO response. Results on the excited state absorptions in these compounds are also presented.     

Organic photosensitizers with N-carboxymethyl pyridinium acceptor/anchoring group for dye-sensitized solar cells

Four new organic dyes with N-carboxymethyl pyridinium as electron acceptors/anchoring groups were designed and synthesized. The optical and electrochemical properties were characterized by UV–vis, fluorescence spectroscopy and cyclic voltammetry. The absorption spectra of the four pyridinium dyes were in the range of 450–650 nm. The dye with triphenylamine as the electron donor shows a solar-energy-to-electricity conversion efficiency (η) of 2.33% in comparison with the reference Ru-complex (N719 dye) with a η value of 5.45% under the same experimental conditions. The dye with phenoxazine as the electron donor gives broad IPCE spectra in the range of 400–750 nm. All these new dyes are simple in structure, very easy to synthesize, and gives high V_oc.     

Influence of cluster composition on NLO properties of neutral cubane-like heterothiometallic clusters

A series of new candidates as nonlinear optical materials, tetra-nuclear heterobimetallic clusters [MOS₃M₃′Y(PPh₃)₃] (M = Mo, M′ = Ag, Y = Br 1; M = W, M′ = Ag, Y = I 2; M = Mo, M′ = Cu, Y = I 3; M = W, M′ = Cu, Y = I 4), have been synthesized by newly developed ligand-redistribution reaction for third-order nonlinear optical (NLO) studies. Single-crystal X-ray diffraction shows that clusters [MoX(μ₃-S)₃(μ₃-Br)(AgPPh₃)₃] 1 and [WX(μ₃-S)₃(μ₃-I)(CuPPh₃)₃] 4 (X = O_0.5S_0.51, O 4) adopt an isomorphous neutral cubane-like skeleton. Their optical nonlinearities were measured by Z-scan technique with an 8 ns pulsed laser at 532 nm. These clusters were found to exhibit effective nonlinear absorption, self-focusing effects and large optical limiting capabilities. The effective NLO susceptibilities χ⁽³⁾ and the corresponding second-order hyperpolarizabilities γ of these clusters are also reported. The influence of cluster composition on NLO properties has been discussed accordingly.     

Synthesis and third order optical nonlinearity studies of the donor–acceptor conjugated polymer,poly(2-[3,4-didodecyloxy-5-(1,3,4-oxadiazol-2-yl)thiophen-2-yl]-5-phenyl-1,3,4-oxadiazole) and a polymer/TiO2 nanocomposite

A donor–acceptor conjugated polymer (PDOThPOD) containing 3,4-didodecyloxythiophene and (1,3,4-oxadiazolyl)benzene units is synthesized by using precursor polyhydrazide route. Cyclic voltammetry studies reveal that the polymer possesses a low-lying LUMO energy level (?3.57 eV). A nanocomposite of polymer PDOThPOD and nano TiO₂ is also prepared. The linear optical properties of PDOThPOD and the nanocomposite are studied using UV–vis absorption spectroscopy and fluorescence emission spectroscopy. z-scan technique is used to study the third order nonlinear optical properties of the polymer and nanocomposite films. Both polymer and nanocomposite films show a strong optical limiting behavior. The value of nonlinear absorption coefficient (β) is found to be of the order of 10^?7 m/W, indicating that these materials are potentially suited for fabricating optical limiters.     

Synthesis of electrochemically and thermally stable amorphous hole-transporting carbazole dendronized fluorene

A novel amorphous hole-transporting carbazole dendrimer, 2,7-bis[3,6-di(carbazol-9-yl)carbazol-9-yl]-9,9-bis-n-hexylfluorene (G2CF), was synthesized by a divergent approach involving bromination and Ullmann coupling reactions. G2CF showed UV–vis absorption bands at 304 and 332 nm in chloroform solution and the photoluminescence spectra showed a maximum peak at 373 nm in a bluish-purple region. Differential scanning calorimetry (DSC) and cyclic voltammetry (CV) analysis revealed G2CF was an electrochemically and thermally stable amorphous material with a high glass transition temperature (T_g) of 237 °C. The organic light-emitting device having the structure of ITO/G2CF/Alq₃/LiF:Al exhibited a bright green emission with a maximum luminescence of 11,000 cd/m² at 16 V and a turn-on voltage of 5.4 V.     

Synthesis,photophysics, electrochemical and electroluminescent properties of divinylene compounds with phthalimide moieties

Three new divinylene compounds F, C and P which contained fluorene, carbazole and phenylene as central unit, respectively, and terminal phthalimide groups were synthesized by Heck coupling. The alkyl or alkoxy chains attached to the central unit as well as the cyclohexyl ring attached to the terminal phthalimides render the samples very soluble in common organic solvents. They had relatively low glass transition temperatures (T_g's), being in the range of 54–81 °C. P was stable up to about 200 °C while F and C were stable up to 300 °C. The absorption maximum was located at 387–440 nm with optical band gap of 2.48–2.56 eV. They emitted blue-green light with emission maximum at 484–562 nm. P showed the most red-shifted absorption and emission maximum. The HOMO and LUMO levels of the compounds, estimated from their cyclic voltammograms, were −6.42 to −5.58 eV and −3.06 to −2.99 eV, respectively, from which their band gaps were estimated to be 3.36 eV, 2.68 eV, and 2.52 eV. The emission spectra and performance of the EL devices, using blends of the compounds and PVK as emitting layer, also depended strongly on the compounds. The P device emitted green light (530 nm) with maximal luminance and current efficiency being at 1358 cd/m² and 0.57 cd/A, while those of the F device were green-blue (490 nm), 593 cd/m² and 0.22 cd/A.     

Synthesis,X-ray structure and luminescent properties of a new 1D terbium(III) coordination polymer based on 2,4-dichlorophenoxyacetate and 4,4′-bipyridine

A new 1D terbium coordination polymer, {[Tb(2,4-dcpa)₃(H₂O)₂]·(4,4′-bpy)_1.5(H₂O)₂}_n (1) [2,4,-dcpa = 2,4-dichlorophenoxyacetate, 4,4′-bpy = 4,4′-bipyridine], was prepared by hydrothermal synthesis and characterized by IR spectroscopy, elemental analysis, thermogravimetric analysis (TGA) and single-crystal X-ray diffraction. Complex 1 exhibits an infinite chain structure with a {Tb₂(2,4-dcpa)₆(H₂O)₄} dimeric repeat unit. Each Tb³⁺ ion is nine-coordinated to two water molecules, one monodentate carboxylate group and four bridging carboxylate groups in which the carboxylate groups are bonded to the terbium ion in one modes: the chelating–bridging tridentate. Three-dimensional fluorescence spectra of 1 were detected at room temperature under the excitation and the emission wavelengths in the range of 420–750 nm with the interval of 5 nm. The lifetime of 1 in solid-state at room temperature up to 1.132 ms. On the other hand, poor luminescence efficiency has been noted for the Tb³⁺-2,4-dcpa complex.     

Theoretical studies on the spectroscopic properties of a series of halide Zinc (II) complexes with pyridinylimine and pyridinylmethylamine derivatives

The ground structures of pyridinylimine derivatives (L1-a = N-(pyridin-2-ylmethylene)aniline and L1-b = N¹,N¹-(dimethyl-N⁴-pyridin-2-ylmethylene)benzene-1,4-diamine) and pyridinylmethylamine derivatives (L2-a = N-(pyridin-2-ylmethyl)aniline and L2-b = N¹,N¹-(dimethyl-N⁴-pyridin-2-ylmethy)benzene-1,4-diamine) and their corresponding Zn (II) complexes ([Zn(L1-a)Cl₂] (A), [Zn(L1-b)Cl₂] (B), [Zn(L2-a)Cl₂] (C), and [Zn(L2-b)Cl₂] (D)) are optimized at three DFT levels, i.e., B3LYP, B3PW91, and M06. The spectroscopic properties are calculated using time-dependent density functional theory (TD-DFT) in gas and in solution. The occupied orbitals involved in the transitions have mixed character of the Cl atom p orbital and ligand-based π orbital, while the lowest unoccupied molecular orbital (LUMO) presents π* orbital character. Two UV–Vis absorption peaks located at 252 and 353 nm are assigned to (p, π) → π* transition with mixed intraligand charge-transfer (ILCT)/ligand–ligand charge-transfer (LLCT) character and π → π* transition with ILCT character for complex A, respectively. With respect to complex B, the absorption bands show red shift with two peaks at 281 and 470 nm with the appearance of an electron-releasing group (–N(CH₃)₂) because the energy gap (ΔE|HOMO–LUMO|) is decreased. Red shift phenomenon is also observed between other two complexes C and D. Comparison between theoretical and experimental results for the structures and spectra is discussed in detail.     

Preparation and luminescent characteristics of Sr3RE2(BO3)4:Dy (RE = Y, La, Gd) phosphors for white LED

Dysprosium-activated Sr₃RE₂(BO₃)₄ (RE = Y, La, Gd) phosphors were synthesized by a high temperature solid-state reaction method. The phase uniformity of the phosphors was characterized by X-ray powder diffraction (XRD) and the luminescence characteristics were investigated. The excitation spectra at 575 nm emission show strong spectral bands in the region of 300-500 nm. The emission spectra of the phosphors with 365 nm excitation show three bands centered at 484 nm, 575 nm and 680 nm, which originate from the transitions of ⁴F_9/2 → ⁶H_15/2, ⁴F_9/2 → ⁶H_13/2 and ⁴F_9/2 → ⁶H_11/2 of Dy³⁺, respectively. The effect of Dy³⁺ concentration on the emission intensity of the phosphors was investigated. The fluorescence decay curves for ⁴F_9/2 → ⁶H_13/2 excited at 365 nm and monitored at λ_em of 575 nm were measured. The decay times decreased slowly with increasing Dy³⁺ doping concentration due to a trap capturing to resonance fluorescence transfer of the activated ions and due to the exchange interactions between activated ion pairs. In order to determine the type of interaction between activated ions, the concentration dependence curves (lg(I/x) versus lg x) of Sr₃RE₂(BO₃)₄:Dy³⁺ (RE = Y, La, Gd) were plotted. The concentration quenching mechanism of the ⁴F_9/2 → ⁶H_13/2 (575 nm) transition of Dy³⁺ is the d-d interaction. All results indicate these phosphors are promising white-color luminescent materials.     

Effect on response time and diffraction efficiency of co-usage azo dye and carbon nanoparticle in nematic liquid crystal

In this work, the formation of the photo-induced grating and nonlinear optical properties such as diffraction efficiency (η), refractive index modulation (Δn), nonlinear index coefficient (n₂) of nematic liquid crystal (E7) doped by azo dye (Methyl Red) and C60 have been investigated by diffraction grating measurements. Diffraction efficiencies of 441 nm pump and 632 nm probe beams were measured in two-wave mixing experiment. Maximum diffraction efficiency was found 26% doped with both 1% MR and 0.5% C60, while cells without C60 had maximum diffraction efficiency of 19% under 30 mW laser illumination. Rise time was found to increase with Methyl Red concentration. The nonlinear index coefficient, n₂, was calculated to be 11 × 10⁻³ cm²/W and highly depend on MR concentration.     

Facile synthesis of polyaniline nanofibers using pseudo-high dilution technique

A new approach for the synthesis of polyaniline nanofibers under pseudo-high dilute conditions in aqueous system has been developed. High yield nanoscale polyaniline fibers with 18–110 nm in diameter are readily prepared by a high aniline concentration 0.4 M oxidation polymerization using ammonium persulfate (APS) as an oxidant in the presence of hydrochloric acid (HCl), perchloric acid (HClO₄), (1S)-(+)-10-camphorsulfonic acid (CSA), acidic phosphate PAEG120 (PA120) and sulfuric acid (H₂SO₄) as the dopants. The novel pathway always produces polyaniline nanofibers of tunable diameters, high conductivity (from 10⁰ to 10¹ S/cm) and crystallinity.     

Synthesis of the pyrrolo[3,2-b]pyrrole-based copolymer with enhanced open circuit voltage

A new accepter unit, pyrrolo[3,2-b]pyrrole-2,5-dione, was prepared and utilized for the synthesis of the conjugated polymer containing electron donor–acceptor pair for OPVs. Pyrrolo[3,2-b]pyrrole-2,5-dione unit, regioisomer of the known pyrrolo[3,4-c]pyrrole-1,4-dione, is originated from the structure of stable synthetic pigment. The new conjugated polymer with pyrrolo[3,2-b]pyrrole-2,5-dione, thiophene and carbazole was synthesized using Suzuki polymerization to generate P1. The solid thin film of P1 shows absorption band with maximum peaks at 374 and 548 nm, and the absorption onset at 679 nm, corresponding to band gap of 1.83 eV. The field-effect hole mobility of P1 is 2.2 × 10⁻⁵ cm²/Vs. The device based on the polymer:PCBM (1:2) blend without thermal treatment showed a V_OC of 0.82 V, a J_SC of 6.28 mA/cm², and an FF of 0.39, giving a PCE of 2.00%.     

Diphenylthiocarbazone (dithizone)-assisted solvothermal synthesis and optical properties of one-dimensional CdS nanostructures

One-dimensional (1D) cadmium sulfide (CdS) nanostructures with various aspect ratios were successfully synthesized by a diphenylthiocarbazone (dithizone)-assisted solvothermal method. The results showed that the dithizone-assisted synthesized samples had larger aspect ratio than that prepared in the absence of dithizone, and CdS nanowires with the highest aspect ratio were obtained with an appropriate dithizone amount (0.03 g/50 ml ethylenediamine in the present system). All the 1D CdS nanostructures were in hexagonal wurtzite phase. The as-synthesized large-scale CdS nanowires were in diameters ranging from 70 to 80 nm, length up to 20 μm, and aspect ratios of 250-285. Further characterization indicated that the CdS nanowires were single crystalline with a preferential growth orientation of [0 0 2], c-axis. Two optical absorption peaks were observed at about 488 nm and 502 nm for the CdS nanowire sample with high aspect ratio in the optical absorption spectroscopy, which could be attributed to the nanometer effect of nanowires. It was found that the additive dithizone was a crucial factor in controlling the morphology and optical properties of the 1D CdS nanostructures. The growth mechanism of 1D CdS nanostructure and the effects of dithizone in the present system were discussed.     

Fine tuning the HOMO energy levels of polythieno[3,4-b]thiophene derivatives by incorporation of thiophene-3,4-dicarboxylate moiety for photovoltaic applications

To lower the HOMO (highest occupied molecular orbital) energy level of polythieno[3,4-b]thiophene (∼−4.5 eV), a series of ester-functionalized polythieno[3,4-b]thiophene derivatives (P1–P3) were designed and synthesized by Stille cross coupling reaction. The resulting copolymers exhibited broad and strong absorption bands from visible to near infrared region with low optical band gaps of 1.23–1.42 eV. Through cyclic voltammetry measurements, it was found that the HOMO energy levels of the copolymers gradually decreased with increasing the content of the thiophene-3,4-dicarboxylate moiety, i.e. −4.91 eV for P1, −5.00 eV for P2, and −5.11 eV for P3. Preliminary photovoltaic properties of the copolymers blended with [6,6]-phenyl-C₆₁-butyric acid methyl ester (PCBM) as electron acceptor were investigated. Among the three copolymers, P1 exhibited the best photovoltaic performance with an open circuit voltage (V_oc) of 0.54 V, a short circuit current density (I_sc) of 3.3 mA/cm², a fill factor (FF) of 0.57, and a power conversion efficiency (PCE) of 1.02%. A high V_oc up to 0.71 V was achieved in the solar cell based on a P3:PCBM blend.