Electrical properties of polyvinylcarbazole-tetracyanoquinodimethane charge transfer complexes

Electrical properties of polyvinylcarbazole-tetracyanoquinodimethane (PVK:TCNQ) charge transfer complexes were investigated as a function of the composition of the mixture, temperature, pressure and the method of sample preparation. It was shown that the electrical conductivity of the PVK:TCNQ complex (for TCNQ content <10% by weight) increased only slowly with increasing concentration of TCNQ and was only slightly higher than the conductivity of pure PVK. At higher TCNQ concentrations however an abrupt increase of the complex conductivity was observed. This effect may be attributed to the formation of semi-conductive tracks composed of uncomplexed neutral TCNQ molecules. The electrical conductivity of PVK:TCNQ complex was lower than the conductivity of TCNQ alone. The activation energy for electrical conductivity in the complex decreased with increasing TCNQ concentration from 0.99 eV for pure PVK to 0.37 eV for PVK:TCNQ (6:1) complex. The high field conductivity of the PVK:TCNQ complex could be explained by using the Poole-Frenkel model.     

The excited states of some organic charge transfer complexes studied by modulation excitation spectrophotometry

The excited states of some complexes between polycyclic aromatic hydrocarbons and chloranil dissolved in polymethylmethacrylate have been studied with a modulation excitation spectrophotometer. New bands similar to but slightly shifted in position as compared to the T₁–T₃ transition of the aromatic hydrocarbon are observed. Regressional analysis points to the new bands arising from transitions from a level in the chloranil to the T₃ level of the hydrocarbon. An enhancement of the T₁–T₃ bands of the hydrocarbon occurs in the complex. Other bands are also seen which are believed to be due to new levels of the complex which cannot be identified with local levels of the hydrocarbon or chloranil.     

Positron annihilation studies of some charge transfer molecular complexes

Positron annihilation lifetimes were measured for some solid charge transfer (CT) molecular complexes of quinoline compounds (2,6-dimethylquinoline, 6-methoxyquinoline, quinoline, 6-methylquinoline, 3-bromoquinoline and 2-chloro-4-methylquinoline) as electron donor and picric acid as an electron acceptor. The infrared spectra (IR) of the solid complexes clearly indicated the formation of the hydrogen-bonding CT-complexes.

The annihilation spectra were analyzed into two lifetime components using PATFIT program. The values of the average and bulk lifetimes divide the complexes into two groups according to the non-bonding ionization potential of the donor (electron donating power) and the molecular weight of the complexes. Also, it is found that the ionization potential of the donors and molecular weight of the complexes have a conspicuous effect on the average and bulk lifetime values. The bulk lifetime values of the complexes are consistent with the formation of stable hydrogen-bonding CT-complexes as inferred from the IR-spectral data.     

Vibrational spectra of the charge transfer complexes between organic sulfides and iodine

I.r. spectra of the charge transfer complexes between nine organic sulfides (as well as diethylselenide) with iodine were recorded between 1500 and 400 cm⁻¹ in CS₂ and CCl₄ solutions and in the region 600-50 cm⁻¹ in C₆H₁₂ and C₆H₆ solutions. Raman spectra of the complexes were recorded below 600 cm⁻¹. For each system, i.r. and Raman bands in the 200-160 cm⁻¹ were assigned to the II stretching mode of the complex. Additional i.r. bands below 160 cm⁻¹, absent in Raman, were ascribed to intermolecular SI stretching vibrations. The integral intensities of these bands were determined and correlated with the thermodynamic functions. Some Raman active fundamentals of 1,4-dithiane became i.r. active in the iodine complex in accordance with a break down of the C₂h symmetry. A force constant calculation was carried out for the dimethylsulfide-iodine complex and simplified calculations of the three point mass models were made for all the systems.     

Positronium inhibition and quenching by organic electronic acceptors and charge transfer complexes

Positron lifetime measurements were performed on a series of organic electron acceptors and charge-transfer complexes in solution. The acceptors cause both positronium (Ps) inhibition (with maybe one exception) and quenching, but when an acceptor takes part in a charge-transfer complex the inhibition intensifies and the quenching almost vanishes. The reaction constants between ortho-Ps and the acceptors were determinded to be: 1.5 × 10¹⁰ M⁻¹ s⁻¹ for SO₂ in dioxane 3.7 × 10¹⁰ M⁻¹ s⁻¹ for SO₂ in n-heptane, 3.4 × 10¹⁰ M⁻¹ s⁻¹ for tetracyanoquinodimethane in tetrahydrofurane and 1.6 × 10¹⁰ M⁻¹ s⁻¹ for tetracyanoethylene in dioxane. From the ortho-Ps lifetimes in solutions containing charge-transfer complexes complexity constants were determined that were in reasonable agreement with constants obtained from optical data. The influence of acceptors and charge-transfers complexes on the Ps yield was interpreted in terms of the spur reaction model of Ps formation. Correlation was also made to gas phase reaction between electron acceptors and free electron, as well as to pulse radiolysis data.     

Spectroscopic studies of charge transfer complexes between colchicine and some pi acceptors

Charge transfer complexes between colchicine as donor and pi acceptors such as tetracyanoethylene (TCNE), 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ), p-chloranil (p-CHL) have been studied spectrophotometrically in dichloromethane at 21 degrees C. The stoichiometry of the complexes was found to be 1:1 ratio by the Job method between donor and acceptors with the maximum absorption band at a wavelength of 535, 585 and 515 nm. The equilibrium constant and thermodynamic parameters of the complexes were determined by Benesi-Hildebrand and van't Hoff equations. Colchicine in pure form and in dosage form was applied in this study. The formation constants for the complexes were shown to be dependent on the structure of the electron acceptors used.     

Spectrophotometric study of the charge transfer complexes of some pharmaceutical butyrophenones

The molecular interactions between haloperidol and droperidol as electron donors and each of iodine; 7,7,8,8-tetracyanoquinodimethane (TCNQ); 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ); tetracyanoethylene (TCNE); 2,4,7-trinitro-9-fluorenon (TNF); and 2-3-5-6-tetrabromo-1,4-benzoquinone (Bromanil) as acceptors have been investigated spectrophotometrically. Different variables affecting the reaction were studies and optimized. Beer's law was obeyed in a concentration limit of 2.5-2500 mug ml(-1) for the studied drugs with various acceptors used. Electron affinities (E(A)) of the acceptors were found to correlate with both the time required for maximum colour formation and the molar absorptivities of haloperidol and droperidol. A Job's plot of the absorbance versus the molar ratio of the drugs to iodine indicated 1:1 ratio. The proposed methods were found to be rapid and sensitive and may be applied for estimation of named drugs in pharmaceutical dosage forms without interferences from the common additives encountered. Percentage recoveries ranged from 99.1-102.2%.     

Structural and magnetic properties of a novel ferrocenyl-diiodine charge transfer complex

The reaction of 4-ferrocenyl-1,3-dithiole-2-thione with diiodine affords an unprecedented "double" charge-transfer complex; the highly ordered ferrocenium units are held by a supramolecular polyiodide chain, and the material shows evidence of the formation of zigzag magnetic chains below 2 K.     

Simple charge transfer complexes of some new and of some known heterocyclic compounds of selenium and tellurium

Charge transfer (CT) complexes (1:1) of 2,5-dihydrotellurophene and the 3-methyl and 3,4-dimethyl compounds with TCNQ and tetrachlorobenzoquinone (TCB) are reported. The organotellurium compounds failed to give complexes with p-dinitrobenzene (DNB). The variation of solid state (disc) conductivity with temperature and as a function of methyl substituents is considered. The complexes show semi-conducting behaviour and a consideration of these data, together with IR and UV spectroscopic data, in comparison with those for 1,3-dihydro-2-telluraindene given the following order of donor power with respect to TCNQ:

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With respect to a given donor, the order to acceptor power is TCNQ> TCB> DNB.

1,3-Dihydro-2-selanaindene forms a complex with TCNQ. The molecular ionisation potential of the selanaindene is 7.4 eV (by mass spectroscopy) and it has been shown that the compound may be electrochemically oxidized to materials such as C₈H₈SePF₆.

New quinoxalino-1-chalcogenacyclopentanes are reported; namely those derived from selenium, and for the 7,8-dimethyl series, those based on both selenium and tellurium. Their preparation and characterisation are described, and their chemistry shown to be strongly analogous to that of quinoxalino-1-telluracyclopentane. CT complexes of the new Se^II and Te^II compounds (1:1) are prepared with TCNQ which are believed to be strongly ionic.     

Electrical and dielectric properties of charge transfer complexes: Interactions between norfloxacin and ciprofloxacin with picric acid and 3,5-dinitrobenzoic acid

Semiconductor behavior was observed for all three studied complexes. The dielectric constant for [(Nor)(PA)], [(Cip)(PA)], and [(Nor)(DNB)] seems to be frequency independent at high frequency, that may be attributed to low mobility of charge carriers which can not follow the applied field.     

Photochemical and photophysical properties of ion-pair charge transfer complexes for all-optical information processing

The photochemical and photophysical properties of ion-pair charge transfer (IPCT) complexes comprising of 4,4′-bipyridinium and various counter ions have been reviewed. Quantum chemical and thermodynamic properties of IPCT complexes are summarized. IPCT complexes of 4,4′-bipyridinium with tetraphenylborate derivatives showed specific absorption and fluorescence properties. The photoinduced electron transfer from a counter anion to 4,4′-bipyridinium cation occurred within less than 100 fs upon excitation of IPCT complexes. The back electron transfer was controlled by changing counter anions and/or microenvironments. The transient absorption spectroscopy showed the ultrafast back electron transfer between 4,4′-bipyridinium and iodide in less than 2 ps. The absorption spectra of reduced 4,4′-bipyridinium derivatives were controlled over a broad range covering from visible to optical telecommunication wavelength. This phenomenon was applied to all-optical light modulation based on the guided wave mode devices composed of a photoresponsive polymer layer and a low-refractive-index polymer layer.     

Conformationally controlled intramolecular charge transfer complexes

Trans-1-acceptor-2-donor-substituted cyclohexanes (1), as well as their 4- (or 5-)methyl-substituted homologues (2), have been prepared and are shown to form intramolecular charge-transfer (donor-acceptor) complexes. These weak complexes are turned on and off by the chair-chair interconversion of the cyclohexane ring. The CT absorptions have been measured and the equilibrium constants for the ring reversal have been determined by UV/vis spectroscopy at 298 K, as well as by NMR spectroscopy at two temperatures: at 183 K, by direct comparison of signals due to the two chair conformations, and at 300 K, by comparison of calculated and measured widths of the alpha-proton signals. The Gibbs free energies assigned to the donor-acceptor interactions range between 0 and -1 kcal mol(-1). A crystal structure of one of the complexes (1b) confirms the intramolecular donor-acceptor alignment and interaction. The regioisomers of the methyl-substituted complexes were characterized by NOE interaction between the methyl and an alpha-proton cis to it.     

A thermodynamic study of the charge transfer complexes of MV with some macrocyclic hosts

Formation of charge transfer complexes of methyl viologen, MV, and hosts (1?C3) in ethanol were studied using UV?Cvisible spectrophotometry. The stability constants and the thermodynamic parameters of the resulting 1:2 (MV:host ratio) complexes were determined. All charge transfer complexes formed were enthalpy destabilized, but entropy stabilized. The effect of donor atoms, their orientation, the substituents, flexibility and the cavity size of the crown ethers on the formation constants and thermodynamic parameters will be discussed.     

Electrical and spectral properties of organic salts formed from BEDT-TTF and magnetic anions

Spectral and electrical investigations of the semiconducting (BEDT-TTF)₂W₆O₁₉ and the metal-like (BEDT-TTF)₆(Mo₈O₂₆)(DMF)₃ salts were performed. The vibrational and electronic spectra of the crystalline samples were analysed and assignment of the vibrational features was proposed. The temperature evolution of the vibrational spectra of the (BEDT-TTF)₂W₆O₁₉ salt was discussed.     

PCILO Calculations on charge transfer complexes

The equilibrium distances of the complex components and the stabilization energies were calculated for the molecular complexes ethylene–fluorine, ethylene–chlorine, tetracyanoethylene–benzene, tetracyanoethylene–durene, and quinone–hydroquinone using the PCILO method. The results are compared with the experimental values and the theoretical predictions of the CNDO /2 method.     

Electrical conductivity,spectral and magnetic properties of some transition metal complexes derived from dimedone bis(4-phenylthiosemicarbazone)

Summary Co^II, Ni^II, Cu^II, Zn^II, Cd^II and U^VIO₂ complexes of 5, 5-dimethyl-1, 3-cyclohexanone bis(4-phenylthiosemicarbazone), H₂CPT, have been characterized by elemental analysis, i.r. and reflectance spectral studies, and magnetic moment measurements. I.r. spectra show that H₂CPT gives rise to dibasic quadridentate SNNS donor. A square-planar structure is proposed for the copper(II) complex and octahedral for cobalt(II) and nickel(II) complexes according to the magnetic and electronic spectral data. The electrical conductivities of H₂CPT and its CO^II, Ni^II, Cu^II and Cd^II complexes were measured. The positive temperature coefficient (d/dT) and the higher activation energies of H₂CPT and its Cd^II and Cu^II complexes is evidence of their semiconducting character.     

Spectroscopic study on charge transfer molecular complexes of pyrazole derivatives with some pi-electron acceptors

Charge transfer molecular complexes of some pyrazole donors (pyrazole, 4-methylpyrazole, 3-methylpyrazole and 3,5-dimethylpyrazole) with 2,3-dichloro-5,6-dicyano-1,4-p-benzoquinone and tetracyanoethylene as pi-electron acceptors have been studied in CH2Cl2 at 25 degrees C. Spectral characteristics and stability constants of the formed charge transfer (CT) complexes are discussed in terms of the nature of donor and acceptor molecular structure, as well as in relation to solvent polarity. Thermodynamic parameters (deltaH, deltaG and deltaS) associated with CT complex formation are also examined. It was concluded that the formed CT complexes are of n-pi type with 1:1 (D:A) composition.     

Preparation and IR-spectroscopic study of charge transfer complexes of naphthalene derivatives with some tri- and di-nitrobenzenes

The charge transfer complexes of naphthalene and some of its derivatives with some trinitro- and dinitrobenzenes are prepared and investigated by irspectroscopy. The shifts in the bands due to functional groups as well as the _CH bands of both donor and acceptor are found to be indicative for the type of bonding in the charge transfer complex.

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Darstellung und IR-spektroskopische Untersuchungen an Charge Transfer Komplexen von Naphthalinderivaten mit Di- und Tri-nitrobenzolen

Zusammenfassung Aus den Verschiebungen der Bandenlagen bei der Komplexierung, bzw. aus der Abhängigkeit der Bandenlagen von den funktionellen Gruppen, wird der Bindungstyp der Charge-Transfer-Komplexe ermittelt.