Photophysics and Inverted Solvatochromism of 7,7,8,8-Tetracyanoquinodimethane (TCNQ)

We report the absorption, fluorescence, and Raman spectroscopy of 7,7,8,8- tetracyanoquinodimethane (TCNQ) in a variety of solvents. The fluorescence quantum yields (QYs) of linear alkane solutions are similar to one another, but QY is shown to acutely decrease in other solvents with increasing polarities. The slope of the solvatochromic plot of absorption maxima is inverted from negative to positive with an increase in solvent polarity. A significant change in the frequency of carbon-carbon double bond stretching modes is not observed in Raman spectra of TCNQ in different solvents. The molar absorption coefficient is determined to calculate the oscillator strength of the absorption band. The radiative decay rate constant calculated from the oscillator strength is approximately ten times larger than that elucidated from the fluorescence lifetime and QY. These spectroscopic parameters reveal that the relaxation occurs from a Franck-Condon excited state to a distinct fluorescence emissive state with a smaller transition dipole moment

Application of Certain π-Acceptors for the Spectrophotometric Determination of Alendronate Sodium in Pharmaceutical Bulk and Dosage Forms

Two simple, fast, and accurate spectrophotometric methods for the determination of alendronate sodium are described. The methods are based on charge-transfer complex formation of the drug with two π-electron acceptors 7,7,7,8-tetracyanoquinodimethane (TCNQ) and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) in acetonitrile and methanol medium. The methods are followed spectrophotometrically by measuring the maximum absorbance at 840 nm and 465 nm, respectively. Under the optimized experimental conditions, the calibration curves showed a linear relationship over the concentration ranges of 2–10 μg mL−1 and 2–12 μg mL−1, respectively. The optimal reactions conditions values such as the reagent concentration, heating time, and stability of reaction product were determined. No significant difference was obtained between the results of newly proposed methods and the B.P. Titrimetric procedures. The charge transfer approach using TCNQ and DDQ procedures described in this paper is simple, fast, accurate, precise, and extraction-free

Effects of Graphene/BN Encapsulation, Surface Functionalization and Molecular Adsorption on the Electronic Properties of Layered InSe: A First-Principles Study

By using first-principles calculations, we investigated the effects of graphene/boron nitride (BN) encapsulation, surface functionalization by metallic elements (K, Al, Mg and typical transition metals) and molecules (tetracyanoquinodimethane (TCNQ) and tetracyanoethylene (TCNE)) on the electronic properties of layered indium selenide (InSe). It was found that an opposite trend of charge transfer is possible for graphene (donor) and BN (acceptor), which is dramatically different from phosphorene where both graphene and BN play the same role (donor). For InSe/BN heterostructure, a change of the interlayer distance due to an out-of-plane compression can effectively modulate the band gap. Strong acceptor abilities to InSe were found for the TCNE and TCNQ molecules. For K, Al and Mg-doped monolayer InSe, the charge transfer from K and Al atoms to the InSe surface was observed, causing an n-type conduction of InSe, while p-type conduction of InSe observed in case of the Mg-doping. The atomically thin structure of InSe enables the possible observation and utilization of the dopant-induced vertical electric field across the interface. A proper adoption of the n- or p-type dopants allows for the modulation of the work function, the Fermi level pinning, the band bending, and the photo-adsorbing efficiency near the InSe surface/interface. Investigation on the adsorption of transition metal atoms on InSe showed that Ti-, V-, Cr-, Mn-, Co-adsorbed InSe are spin-polarized, while Ni-, Cu-, Pd-, Ag- and Au-adsorbed InSe are non-spin-polarized. Our results shed lights on the possible ways to protect InSe structure and modulate its electronic properties for nanoelectronics and electrochemical device applications

Effect of rigidity of microenvironment on fluorescence of 7,7,8,8-tetracyanoquinodimethane (TCNQ)

We report the effect of rigidity of microenvironments on the fluorescence quantum yield(QY) of TCNQ dispersed in polymers which have different glass transition temperatures. The fluorescence QY decreases by increasing the temperature, which suggests that the nonradiative decay process is thermally activated. A pronounced ecrease in the fluorescence QY is observed when the transition occurs from the glass state to the rubber state. The fluorescence QYs in solvents that have the similar polarity to PMMA and PVAc are smaller than those for these polymers. It is demonstrated that the nonradiative decay process is accompanied by structural deformation

Unipolarization of ambipolar organic field effect transistors toward high-impedance complementary metal-oxide-semiconductor circuits

Ambipolar organic field effect transistors (OFETs), consisting of a composite of polyhexylthiophene (PHT) and [6,6]-phenyl C61-butylic acid methyl ester (PCBM), was converted into a p- or n-type OFET by insertion of a thin tetracyanoquinodimethane (TCNQ) or tetrathiafluvalene (TTF) buffer layer. The interface in the Au/TCNQ/PHT:PCBM composite transports hole but blocks electron, while the transported carrier was switched to electron with insertion of a TTF layer. The selective transport is probably due to vacuum level matching or temporal doping. High impedance in a complementary metal-oxide-semiconductor inverter was demonstrated with unipolarized ambipolar FETs, resulting in a decrease in the through current

Thin film organic thermoelectric generator based on tetrathiotetracene

Thin films of p- and n- type organic semiconductors for thermo-electrical (TE) applications are produced by doping of tetrathiotetracene (TTT). To obtain p-type material TTT is doped with iodine during vacuum deposition of thin films or by post-deposition doping using controlled exposure to iodine vapors. Thermal co-deposition in vacuum of TTT and TCNQ is used to prepare n-type thin films. The attained thin films are characterized by measurements of Seebeck coefficient and electrical conductivity. Seebeck coefficient and conductivity could be varied by altering the doping level. P-type TTT:iodide thin films with a power factor of 0.52 μWm-1K-2, electrical conductivity of 130 S m-1 and Seebeck coefficient of 63 μV K-1 and n-type TCNQ:TTT films with power factor of 0.33 μWm-1K-2, electrical conductivity of 57 S m-1 and Seebeck coefficient of -75 μV K-1 are produced. Engineered deposition of both p- and n-type thermoelectric conducting elements on the same substrate is demonstrated. A proof of concept prototype of planar thin film TE generator based on a single p-n couple from the organic materials is built and its power generation characterized

Anthracene and TCNQ doping of substituted nickel phthalocyanine: Effects on the electrical and optical properties of spin coated thin films

In this work, we study the controlled doping of thin films of substituted nickel phthalocyanine, NiPcR8, where R=-SC6H13, with anthracene and TCNQ and investigate the effects of the extent of this doping on the optical and electrical properties of NiPcR8 films. Optical constants, namely index of refraction (n) and extinction coefficient (k) have increased for both types of doping, as determined from spectroscopic ellipsometry measurements. Conductivity is shown to increase by about four orders of magnitudes compared to pure NiPcR8 films as a result of anthracene doping while TCNQ has resulted in almost six orders of magnitudes increase in the film’s conductivity

Optical absorption and electrical conductivity of electron acceptor doped poly-3-octylthiophene films

Optical absorption and electrical conductivity measurements of solution-doped poly-3-octylthiophene (P3OT) films were studied. Chloroform solutions of P3OT were doped with the organic electron-acceptors, 2,3-dichloro-5,6-dicyano-l,4-benzoquinone (DDQ) and 7,7,8,8-tetracyanoquinodimethane (TCNQ); and with the inorganic electron acceptor, ferric chloride (FeCl{dollar}\sb3{dollar}). Charge transfer was observed in P3OT solutions doped with FeCl{dollar}\sb3{dollar} and DDQ. TCNQ-doped solutions showed no optical evidence of charge transfer. Thin films of the doped P3OT were examined at various doping levels. Spectroscopic and electrical conductivity measurements of P3OT films, doped with DDQ, TCNQ, and FeCl{dollar}\sb3{dollar}, at different doping levels, are presented. Optical absorption measurements provided information on the degree of charge transfer occurring for the various dopants. Electrical conductivity measurements showed that the conductivity of P3OT increased with the various dopants in the order of TCNQ {dollar}\u3c{dollar} DDQ {dollar}\u3c{dollar} FeCl{dollar}\sb3{dollar}, for the same dopant concentration level. Results are discussed in relation to the electrochemical properties of the prepared films and the structural properties of P3OT