TTF and TCNQ analogues derived from a new benzo-fused thiopyranyl building block

TTF-type and TCNQ-type analogues (9-12) have been prepared from a new benzo-fused thiopyranyl precursor 8. The synthetic conditions of 8 were optimized. An anomaly was observed in the ¹H NMR spectrum of 9. The crystal structures of 9 and 10 show distorted conformations and ordered packing geometries connected by short contacts. Electronic and redox properties of 9-12 were investigated by UV-vis spectroscopy and cyclic voltammetry. Both 9 and 10 exhibited p-type OFET performances.     

Pre-resonance Raman intensity studies of TCNQ and TCNQ−

Pre-resonance Raman spectra have been obtained for TCNQ and LiTCNQ in acetonitrile solution using an Ar⁺—Kr⁺ laser and a tunable rhodamine 6G dye laser. Using the theory of Albrecht and Hutley, we have calculated frequency factors for the intensity variations for several symmetric vibrational modes of each molecule. The observed spectra for TCNQ and LiTCNQ with violet, blue, and green excitation give evidence for B-type resonance enhancement due to vibronic mixing between at least two violet and ultraviolet transitions. The Raman spectra for LiTCNQ with yellow, orange, and red excitation show A-type enhancement due to a single electronic excitation in the near infrared.     

Electrical conduction studies in ferric-doped KHSO4 single crystals

Direct-current conductivity of ferric-doped (138, 267, and 490 ppm) single crystals of KHSO₄ has been studied. The mechanism for the dc conduction process is discussed. It is observed that the ferric ion forms a (Fe³⁺-two vacancies) complex and the enthaply for its formation is 0.09 ± 0.01 eV. It is proposed that each ferric ion removes two protons from each HSO₄ dimer. The conductivity plot shows the presence of intrinsic and extrinsic regions. It is proposed that in the intrinsic region the dimer of HSO^?₄ breaks reversibly to form a long-chain monomer-type structure. The conductivity in the KHSO₄ crystal is proposed to be controlled by the rotation of HSO^?₄ tetrahedra along the axis which contains no hydrogen atom. Isotherm calculation for the trivalent-doped system is applied to this crystal and the results are compared with Co²⁺-doped KHSO₄ crystal. The distribution coefficient of ferric ion in the KHSO₄ single crystal is calculated to be 4.5 × 10^?1. Ferric ion causes tapering in the crystal growth habit of KHSO₄ and it is believed to be due to the presence of (Fe³⁺-two vacancies) complex. The enthalpy values for the various other processes are as follows: enthalpy for the breakage of HSO^?₄ dimer (H_i) = 1.28 ± 0.01 eV; enthalpy for the rotation of HSO^?₄ tetrahedron (H_m) = 0.58 ± 0.01 eV.     

电荷转移复合分子晶体TMPD·(TCNQ)2的电子能带结构及其与NMP·TCNQ和TTF·TCNQ的比较

本文对电荷转移复合分子晶体TMPD·(TCNQ)_2的电子能带进行了计算。在计算中将TMPD及TCNQ分别作为准一维分子柱来处理。所用计算方法为EHMO/LCAO-MO-CO方法。计算结果再次证实我们在前文给出的规律, 即分子晶体能带的位置由其孤立分子相应分子轨道能级的位置决定, 而能带宽度由相邻分子的相应分子轨道间的相互作用决定。本文还对该晶体的能带结构及其与室温电导率的关系进行了讨论, 并与NMP·TCNQ 和TTF·TCNQ晶体的进行比较。     

Oxygen reduction at the interface of nonstoichiometric fluoride single crystals with metal electrodes

Electrochemical measurements are carried out on three-phase boundaries LaF₃:Eu²⁺/Me, oxygen gas, where Me = Ti, Be, Ta, Au and also on the boundaries of CeF₃:Sr²⁺ with Ag-supported Ag and Bi microelectrodes by the methods of linear scan voltammetry, chronoamperometry, and cyclic voltammetry. The conditions beneficial for reduction of oxygen gas, transformations of chemisorbed oxygen, and the appearance of its mobile forms are considered. Results on the interaction of gaseous oxygen with metals in contact with LaF₃:Eu²⁺ single crystals are generalized. The correlation is found between the oxygen reduction potential and the difference of electronegativities Δχ Me-O. The relationship is revealed between the oxygen reduction potential and the Me-Me bond energy by taking into account the structural factor f/k _n, where f is the number of binding electrons and k _n is the coordination number.     

All-valence-electron band structures of infinite stacked poly(TCNQ) and poly(TTF) chains

We have computed the energy band structures of the inifite poly(TCNQ), poly(TCNQ^2?), poly(TTF) and poly(TTF²⁺) chains using the CNDO/2 and where possible the MINDO/2 crystal orbital approximation schemes. The results show a broad conduction band for poly(TCNQ) and a broad valence band for poly(TTF). The bandwidths within the MINDO/2 CO scheme are found to be smaller by roughly a factor of $\text{1}\text{2}$ as compared with those found within the CNDO/2 CO scheme. Our findings are in agreement with a bandwidth of 0.4–0.5 eV for the conduction band of TCNQ—TTF crystals as found by experiments. A brief discussion is given of the k-dependence of the physically interesting bands which is not always simple.     

Dye-sensitized solar cells made from BaTiO3-coated TiO2 nanoporous electrodes

We reported on the preparation of a thin BaTiO₃-coated layer (2.27 nm) on the surface of TiO₂ and its further application in the dye-sensitized solar cells (DSCs). The as-prepared BaTiO₃–TiO₂ films were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and transmission electron microscope (TEM). The performances of the DSCs with and without BaTiO₃ coating were analyzed by cyclic voltammograms (CVs), electrochemical impedance spectroscopy (EIS), and current–voltage measurements. It was found that the BaTiO₃–TiO₂ films with about 12 μm thickness increased the dye adsorption, resulting in increased J_sc. In the meantime, the BaTiO₃ modification on the TiO₂ surface is beneficial to the formation of an energy barrier against the electron transfer from TiO₂ to I₃⁻, providing the increase of V_oc due to the increased electron density in the TiO₂ that is caused by the increased electron lifetime.     

EPR studies of a molybdenyl complex in single crystals of NH4Cl

Electron paramagnetic resonance of [MoOCl₅]^2? has been studied in single crystals of NH₄Cl. At room temperature the interaction of the unpaired electron with both the even and odd isotopes of molybdenum has been observed. The existence of metal-halogen π bonding is established by the observation of the ligand superhyperfine interaction at liquid nitrogen temperatures. Various possible models corresponding to the different spatial configurations of the molybdenyl complex in the lattice are considered to explain the experimentally observed features. The spectra are analysed using the usual spin-hamiltonian corresponding to tetragonal symmetry. The spin-hamiltonian parameters obtained are: g_∥ = 1.964, g_? = 1.945, A_∥ = 75.53 × 10^?4 cm^?1, A_⊥ = 38.42 × 10^?4 cm^?1.     

Production of nickel sulfate single crystals in processing of nickel oxide electrodes of alkaline batteries

[NiSO₄(H₂O) _n ] single crystals were grown by slow cooling and evaporation of a solution for sulfuric acid leaching of the active paste of a nickel oxide electrode from a spent alkaline battery. The crystals were studied by X-ray phase analysis in two measurement configurations (transmission and Bragg-Brentano focusing).     

Highly super capacitive electrodes made of graphene/poly(pyrrole)

We report on the development and characterization of high performance supercapacitor electrodes synthesized using electrophoretic deposition of graphene, upon which the poly(pyrrole)-layer was electropolymerised. The highly capacitive electrode had a specific capacitance of 1510 F g(-1), area capacitance of 151 mF cm(-2) and volume capacitance of 151 F cm(-3) at 10 mV s(-1).     

Adsorption of TTF,TCNQ and TTF-TCNQ on Au(111):An in situ ECSTM study

The adsorption and adlayer structures of tetrathiofulvalene (TTF), tetracyanoquinodimethane (TCNQ) and TTF-TCNQ on Au(111) have been systematically investigated by in situ electrochemical scanning tunneling microscopy (ECSTM) and cyclic voltammetry in 0.1 mol?L?1 HClO4. All the three molecules were found to form well-ordered adlayers in the double-layer potential region of Au(111). For TTF and TCNQ adlayers, (6×3) and (4×7) structures have been observed, respectively. A structural transition was observed on...     

NMR and Raman spectral studies of ammonium hydrogen selenites single crystals

The chemical composition and peculiarities of the structure of a salt that precipitates from aqueous solution of NH₄HSeO₃ at the 25 °C was studied by NMR and Raman spectroscopy methods using the single crystal samples with different heavy water contents. It was proved that this salt is actually monohydrate of hydrogen selenite, NH₄HSeO₃H₂O but not trihydrate of pyroselenite, (NH₄)₂Se₂O₅3H₂O as was assumed previously based on the data cited in the literature.     

EPR studies of VO2+ ions in kainite single crystals

Electron paramagnetic resonance (EPR) spectra of VO2+ ions doped in Kainite (a mineral salt) single crystals and powder were recorded at room temperature at X-band frequencies.The angular variation studies of the spectra indicate that the VO2+ ion enters Mg2+ ion site substitutionally. The principal values of g and A-tensors were determined from the EPR spectral studies. Using these EPR parameters, the molecular orbital bonding parameters of VO2+ ion in the lattice have been evaluated and discussed.     

Drawing of fibers from irradiated polyethylene single crystals

The relationship between the structural defects present in crystalline polymers and the molecular structure of the drawn material is studied by drawing fibers from irradiated polyethylene single crystals. Irradiation introduces a structural defect in the crystal lattice since it generates crosslinks preferentially, the density of which is controlled by the radiation dose. Observations by means of transmission electron microscopy and electron diffraction indicate that fiber drawing occurs by breaking off of single blocks of folded chains and by subsequent thermally activated rearrangement of the molecules in the drawn material. With increasing crosslink density the size of the blocks decreases, and the fibers become increasingly interconnected so that a network of fibers is formed. If the dose is about 10 Mrad, the crosslinks present in the crystals result in the formation of bundles of fibers. Above 35 Mrad the formation of fibers (single fibers as well as bundles) ceases, and the drawn material forms a thin (15 Å), continuous film. The observed change in morphology with increasing dose (crosslink density) is interpreted in terms of the additional bonding forces between adjacent chains due to crosslinks.     

Structure of fibers drawn from polyethylene single crystals

Transmission electron microscopy and electron diffraction were used to study the molecular structure of fibers drawn from polyethylene single crystals at 77, 293, and 383°K. The results suggest that the formation of the fibers occurs by a two-step process. The first step is the breaking off of single blocks of folded chains from the single crystals so that a “string-of-pearls” structure is obtained. If the temperature is sufficiently high this process is followed by the thermally activated rearrangement of the molecules in the drawn fibers so that a “bamboo” structure results.     

Mixed-crystal infrared studies of chain-folding in polyethylene single crystals: Low-temperature and molecular weight studies

Infrared spectra of 40 PEH/1 PED mixed crystals have been obtained at low temperature as a function of the molecular weight of the PED. The band contour in the CD₂ bending region was resolved into crystalline and noncrystalline components by a least-squares fitting of Gaussian-plus-Lorentzian bands. The splittings of the crystalline component were analyzed in terms of the theory for finite chains of coupled oscillators, with the help of normal coordinate calculations for certain structures. Together with some results on n-paraffin mixed crystals, our studies show that (i) the spectroscopic observations are associated with interactions of crystalline stems of a single molecule; (ii) the observed crystalline splittings are incompatible with an essentially “switchboard” model of chain folding; (iii) adjacent reentry folding predominates, with folding along single (110) and (200) planes occurring; and (iv) for high molecular weights of PED double (110) fold planes prevail. These results are seen to be consistent with the morphologies known to be associated with the conditions of crystallization.     

Electroreflectance studies on the excitons in PTS and DCHD single crystals

In polydiacetylene single crystals of PTS [poly-2,4-hexadiyne-1,6-diol-bis(p-toluene sulfonate)] and of DCHD [poly-1,6-di(N-carbazolyl)-2, 4-hexadiyne] electric field modulated reflectance spectra in the range of the π-π* excitations of the polymer indicate considerable delocalization of the electrons along the chain. Shape and size of the excitonic electroreflectance spectra are determined by a large charge transfer component of the excitons. Evaluation of the spectra yields about 20% and 40% charge transfer with excitation to neighbouring π bonds in PTS and DCHD, respectively. Large differences occur in electroreflectance in the range of vibronic excitons pointing to pronounced coupling of the carbazole side group in DCHD to the π electrons of the chain. At higher energy, ?0.48 eV above the lowest exciton transition in both polymers a large electroreflectance signal is observed which is attributed to a band transition.