Investigation on the third order nonlinearity of some organic charge-transfer complexes

The degenerate four wave mixing experiments have been performed in the N, N-dimethylformamide solutions of 3, 4, 9, 10-Tetramethylperylene (TMP) · AsF_6 and (TMP) · PF_6, respectively. The result showed that the two complexes have large nonlinear optical response.     

A comparison of electron-spin resonance spectra in some organic charge-transfer salts

Studies of multiline ESR spectra in ten organic charge-transfer salts give g-tensors which are characteristic of individual molecular ions containing sulphur, nitrogen and smaller atoms. Such nearly universal g-tensors are not found in three salts with molecules containing selenium. These conclusions are supported by some results at variable temperature and hydrostatic pressure.     

Growth,structural, spectral and optical studies on 2,4-dinitrophenol organic single crystal

Single crystals of 2,4-dinitrophenol were grown by slow evaporation solution growth technique in room temperature. Crystallinity of the grown crystal was confirmed by powder X-ray diffraction technique. UV transmission study shows the good optical transmission in the entire visible region. The dielectric loss is very low at high frequency which shows that the crystal contains low level defects. Photoconductivity reveals the positive nature of the photocurrent in these crystals. The powder second harmonic generation test was also carried out using Q-switched Nd:YAG laser.     

Structural, spectral and mechanical studies of bimetallic crystal: cadmium manganese thiocyanate single crystals

A nonlinear optical bimetallic thiocyanate complex crystal, cadmium manganese thiocyanate (CMTC) has been successfully synthesized. The growth of single crystals of cadmium manganese thiocyanate has been accomplished from aqueous solution using slow evaporation method. The presence of manganese and cadmium in the synthesized material was confirmed through energy dispersive spectrum (EDS) analysis. Structural analysis was carried out using powder X-ray diffractometer (PXRD) and crystalline perfection of the grown crystals was ascertained by high-resolution X-ray diffraction (HRXRD) analysis. Fourier transform infrared (FTIR) spectrum was taken to confirm the functional groups. The transmittance spectrum of the crystal in the UV–visible region has been recorded and the cutoff wavelength has been determined. The dielectric measurements for the crystals were performed for various frequencies and temperatures. The mechanical properties were evaluated by Vickers microhardness testing, which reveals hardness and stiffness constant of the crystals.     

Physicochemical and luminescence properties of some organic complexes of europium and terbium

A series of new chelates of europium and terbium with a high quantum yield of the individual luminescence lines has been synthesized. Absorption and luminescence spectra of the synthesized compounds, and values of the lifetime of the excited state and the quantum yield of the most intense luminescence lines, are given for solutions and crystals.     

Polarization in organic molecular crystals and charge-transfer salts

Polarization in insulators is a general phenomenon that extends over nanometer distances. Two special cases illustrate recent theoretical progress. Polarization energies of localized charges in organic molecular crystals exceed the bandwidth and redistribute the charge density. A systematic treatment of electronic polarization is summarized in the limit of zero intermolecular overlap for pentacene crystals or thin films on metallic substrates, with special attention to the transport gap for producing a separated electron–hole pair and the optical dielectric tensor of the crystal. When overlap cannot be neglected, the general formulation of polarization in extended insulators is in terms of the exact ground state's phase. This formulation is applied to organic charge-transfer (CT) salts whose correlated electronic structure is described by one-dimensional Peierls–Hubbard models. Near the Peierls instability, coupling to lattice modes generates large peaks in the dielectric response that is primarily due to lattice vibrations. Comparisons with experiment are mentioned for both organic molecular crystals and CT salts.     

Electronic,structural and chemical effects of charge-transfer at organic/inorganic interfaces

During the last decade, interest on the growth and self-assembly of organic molecular species on solid surfaces spread over the scientific community, largely motivated by the promise of cheap, flexible and tunable organic electronic and optoelectronic devices. These efforts lead to important advances in our understanding of the nature and strength of the non-bonding intermolecular interactions that control the assembly of the organic building blocks on solid surfaces, which have been recently reviewed in a number of excellent papers. To a large extent, such studies were possible because of a smart choice of model substrate-adsorbate systems where the molecule-substrate interactions were purposefully kept low, so that most of the observed supramolecular structures could be understood simply by considering intermolecular interactions, keeping the role of the surface always relatively small (although not completely negligible). On the other hand, the systems which are more relevant for the development of organic electronic devices include molecular species which are electron donors, acceptors or blends of donors and acceptors. Adsorption of such organic species on solid surfaces is bound to be accompanied by charge-transfer processes between the substrate and the adsorbates, and the physical and chemical properties of the molecules cannot be expected any longer to be the same as in solution phase. In recent years, a number of groups around the world have started tackling the problem of the adsorption, self- assembly and electronic and chemical properties of organic species which interact rather strongly with the surface, and for which charge-transfer must be considered. The picture that is emerging shows that charge transfer can lead to a plethora of new phenomena, from the development of delocalized band-like electron states at molecular overlayers, to the existence of new substrate-mediated intermolecular interactions or the strong modification of the chemical reactivity of the adsorbates. The aim of this review is to start drawing general conclusions and developing new concepts which will help the scientific community to proceed more efficiently towards the understanding of organic/inorganic interfaces in the strong interaction limit, where charge-transfer effects must be taken into consideration.     

Synthesis,spectral studies,and catalytic and antibacterial activity of Ru(II) complexes with coordinated amides

Twelve Ru(II) complexes with coordinated amides were synthesized and characterized by elemental, IR, ¹H, ¹³C, ³¹P NMR, mass, and electronic spectral analysis, along with magnetic and conductance measurements. Molecular formulas and octahedral structures have been tentatively proposed. These complexes were used as catalysts for the hydrolysis of rivastigmine and neostigmine. The hydrolyzed products were coupled with 3-methyl benzothiazolinone hydrazone reagent in the presence of sodium metaperiodate and the resulting colored products were determined spectrophotometrically. The yields of hydrolyzed products were found to be 98.47% and 99.75% respectively. All the ligands and Ru(II) complexes were screened for antibacterial activity. Published in Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 6, pp. 867–874, November–December, 2008.     

Luminescent properties of some ternary complexes of europium with thenoyltrifluoroacetone and organic bases

The relative intensity of the fluorescence I and the mean lifetime of the excited state of the europium ion in ternary thenoyltrifluoroacetonate complexes with organic nitrogen-containing bases have been studied. The introduction of a molecule of the base into the complex alters the structure of the spectrum slightly. The mean lifetime of the excited state of the Eu ion is shorter in solutions of the complexes in all organic solvents than in the solid form. There is an approximate correlation between I and for the europium ion in organic solvents.     

Spectro-streak picosecond studies of intramolecular charge-transfer fluorescence

A spectro-streak photometer, an instrument for simultaneously measuring fluorescence intensity, time, and wavelength,I(t, ), with a single picosecond excitation pulse, has been constructed. Two typical and currently highly topical examples of mesurements are discussed. (1) the temporal development of the fluorescence form the intramolecular charge-transfer (ICT) state of the rigid aromatic compound 4,5-(1-methylindolino)3,4-naphthanthracene is studied in the protic solvent hexanol. (2) Propyl chain-linked pyrene/N,N-dimethylaniline is used as the model compound to study conformational changes associated with the transition from a contact ion pair to a sandwich exciplex.     

Mössbauer,magnetic and ir studies of some mononuclear Fe(III) complexes

Mössbauer studies at room temperature and down to liquid nitrogen temperature were supplemented with magnetic and infrared studies of Monochloroferricbis (X-benzoate) and monochloroferricbis (X-chloroacetate). Mössbauer parameters indicate that all the complexes possess high spin configuration in the trivalent and monomeric states. Positive value of V_zz indicates that there is more negative charge in the x-y plane than in along z-axis, suggesting that Fe is penta-coordinated. Molecular weight determination also confirms that the complexes are mononuclear. The effective magnetic moment of the complexes points out to a weak field iron configuration. An attempt has been made to interpret the structure of these complexes on the basis of the measured data.     

Heavy-atom effect on radiative and radiationless transitions in charge-transfer complexes

The quantum yields of fluorescence and phosphorescence and decay times of fluorescence were measured for a series of charge-transfer complexes of hexamethylbenzene (an electron donor) with various electron acceptors containing heavy (halogen) atoms and the rate constants of different radiative and radiationless transitions were determined. It was found that radiative T₁ → S₀ transition, i.e. the phosphorescence, is strongly enhanced by the heavy-atom effect. The mechanism of the heavy-atom enhancement of charge-transfer phosphorescence is discussed and it is concluded that increasing spin- orbit mixing of radiative T₁ → S₀ charge-transfer transition with singlet-singlet, locally excited transition of acceptor molecule is responsible for the observed effects.     

Similarities in electronic properties of organic charge-transfer solids and layered cobaltates

The apparently counterintuitive carrier concentration-dependent electronic properties of layered cobaltates have attracted wide interest. Here we point out that very similar carrier-concentration dependence has previously been noted in strongly correlated quasi-one dimensional (quasi-1D) organic charge-transfer solids. The normal states of both families can be understood, over the entire range of carrier concentration of interest, within the extended Hubbard Hamiltonian with significant intersite Coulomb interaction. As with the charge-transfer solids, superconductivity in the cobaltates appears to be limited to bandfilling of one-quarter. We point out further that there exist other families of correlated superconductors, such as spinels, where too strong correlations, geometric lattice frustration and bandfilling of one-quarter seem to be the essential features of the unconventional superconductors.     

Strong localization in conducting Langmuir-Blodgett films of quasi-one-dimensional charge-transfer complexes

The temperature dependence of intragrain conductivity of the Langmuir-Blodgett (LB) films of (C₁₆H₃₃-TCNQ)_0.4(C₁₇H₃₅-DMTTF)_0.6 has been studied by means of measuring the surface acoustic waves (SAW) attenuation in a piezocrystal resonator covered by the LB film. [(C₁₆H₃₃-TCNQ)_0.4(C₁₇H₃₅-DMTTF)_0.6 denotes the surface-active charge-transfer complex of hexadecyltetracyanoquinodimethane (C₁₆H₃₃-TCNQ) and heptadecyldimethyltetrathiofulvalene (C₁₇H₃₅-DMTTF)]. We have found that the intragrain conductivity decreases with decreasing temperature, following σ∝exp(−1/T^1/2) law. According to the theory of electron transport in quasi-one-dimensional disordered systems (Q1D DS) proposed by E.P. Nakhmedov et al. [Sov. Phys. Solid State 31 (1989) 368] and developed by Z.H. Wang et al. [Phys. Rev. B 43 (1991) 4373], this temperature behaviour of the conductivity points to the disorder-induced electron localization within the film grains. Fitting our experimental data to the relations proposed in these references, allowed us to evaluate the electron relaxation times due to scattering by phonons and impurities. Based on structural parameters of the conducting bilayer, we have also estimated the Fermi velocity and density of states at the Fermi level, which enabled us to determine the mean free path and localization length in the film studied.     

Ultrafast photoinduced melting of a spin-Peierls phase in an organic charge-transfer compound, K-tetracyanoquinodimethane

Ultrafast photoinduced phase transition in a spin-Peierls (SP) system of K-tetracyanoquinodimethane (K-TCNQ) was studied by femtosecond (fs) reflection spectroscopy. Photocarriers destabilize the SP phase, resulting in a decrease in molecular dimerization within 400 fs. Such a melting of the SP phase drives three kinds of coherent oscillations. By comparing the oscillations with the Raman bands activated by the dimerization, we show that the oscillation of 20 cm-1 is due to an LO phonon, and it plays an important role for the stabilization of the SP phase.