Ultrasonic and spectroscopic studies on hydrogen bonded complexes of aromatic amine and aryl ketones in n-hexane at 303.15 K

Viscometric and ultrasonic studies have been carried out in n-hexane solutions, containing equimolar concentration from 0.02 to 0.2 M of aromatic ketones and N-methylaniline (NMANI), at 303.15 K and at atmospheric pressure. The ketones studied in the present investigation are acetophenone (ACP), 4-chloroacetophenone (ClACP) and 4-methylacetophenone (MACP). The behaviour of measured ultrasonic velocity (u), density (ρ) and viscosity (η) and also the computed acoustic parameters provide strong evidence for the presence of strong solute-solute interactions in the three ternary systems. Excess molar volume and excess thermo acoustic parameters reveal the existence of hydrogen bonded complexes between the solute molecules, ketones and secondary amine. The variation of these parameters with the concentration shows that the existing interactions are influenced by the structure of components and functional groups of the components involved. An attempt has been made to confirm the formation of 1:1 complexes in these systems through UV-visible spectroscopic method at 303.15 K. The calculated values of formation constants of the charge transfer complexes both by acoustic and optical methods agree satisfactorily. The variation in the values of formation constant reveals that electron releasing substituent in the acetophenone molecule enhances the stability while electronegative substituent decreases the stability of the complex. The negative values of free energy of formation of these three complexes indicate that these complexes are thermodynamically stable.     

Threshold formation of an intermolecular charge transfer complex of a semiconducting polymer

It has been found that the formation of an intermolecular charge transfer complex in the ground electronic state between the model conjugated polymer (poly[2-methoxy-5-(2′-ethyl-hexyloxy)-1,4-phenylene vinylene] (MEH-PPV) and the low-molecular-weight organic acceptor (2,4,7-trinitrofluorenone, TNF) occurs stepwise with an increase in the acceptor concentration in the blend as is observed in the optical absorption spectra of solutions. The threshold dependence of the absorption of the charge transfer complex is attributed to the stepwise change in the concentration of the charge transfer complexes, which is not explained by the standard model describing the optical characteristics of intermolecular charge transfer complexes. A kinematic model has been proposed to explain the threshold increase in the concentration of charge transfer complexes: at low acceptor concentrations, the charge transfer complex is formed primarily on the surface of a polymer coil, whereas as the acceptor fraction in the solution increases, TNF molecules penetrate inside the polymer coils, forming the charge transfer complex with the units of the polymer inside the coil.     

Charge‐transfer complex formations of tetracyanoquinone (cyanil) and aromatic electron donors

Single‐electron oxidants are the primary reagents for investigations of the new oxidants and the development of electron‐accepting materials for application in optoelectronics. Quinones are the well‐known class of the neutral single‐electron oxidants. Here, we present the properties of the strongest neutral electron acceptor of this class tetracyanoquinone (cyanil) and investigate its electron‐accepting strength by analyzing the charge‐transfer complex formations with the aromatic donor molecules. Charge‐transfer complexes of tetracyanoquinone with aromatic electron donors are characterized spectroscopically in solution and isolated as the single crystals. Copyright © 2015 John Wiley & Sons, Ltd.     

Steady state and time-resolved spectroscopic investigations on the photoreactions involved within the electronically excited electron acceptor 9-cyanoanthracene in presence of benzotriazole and benzimidazole donors

The electrochemical, “steady-state” and “time-resolved” spectroscopic investigations were made on the well-known electron acceptor 9-cyanoanthracene (CNA) when interacted with the electron donors benzotriazole (BZT) and benzimidazole (BMI) molecules. Though electrochemical measurements indicate the thermodynamical possibility of occurrences of photoinduced electron transfer reactions within these reacting systems in the lowest excited singlet state (S₁) of the acceptor CNA but the steady-state and time-resolved measurements clearly demonstrate only the triplet-initiated charge separation reactions. It was reported earlier that in the cases of disubstituted indole molecules the occurrences of photoinduced electron transfer reactions were apparent both in the excited singlet and triplet states of the acceptor 9-cyanoanthracene, but the similarly structured present donor molecules benzotriazole (and benzimidazole) behave differently from indoles. The weak ground state complex formations within the presently studied reacting systems appear to be responsible for the observed static quenching phenomena as evidenced from the time-resolved fluorescence studies. Time-resolved spectroscopic investigations demonstrate the formation of the ground state of the reacting components (donor and acceptor) through recombination of triplet ion-pairs via formations of contact neutral radical produced by H-abstraction mechanism.     

Photoinduced energy transfer from the triplet state of naphthalene moiety in the Tb/Eu complexes of a specially designed naphthalene cryptand

The paper reports time-resolved emission and energy transfer (ET) studies of metal ion complexes of a specially designed rigid macrocyclic naphthalene cryptand (L) under different conditions. Complex formation of L with Li⁺ and H⁺ causes an appreciable increase in singlet state quantum yield and lifetime of L implying photoinduced electron transfer (PET) from the cryptand moiety to naphthalene unit in the free L. The system exhibits photoinduced ET at 77 K in its Tb³⁺ and Eu³⁺ complexes with either NO₃⁻¹ or Cl⁻¹ as counter-anion. The extent of ET is higher for the Tb³⁺ complex as compared to that for the Eu³⁺ complex. In both Tb³⁺ and Eu³⁺ complex, the NO₃⁻¹ ions influence the relative orientation of donor (L) and acceptor (Ln³⁺) more in favour of ET than the Cl⁻¹ ions. The rate constants for the ET from the naphthalene moiety of L to the acceptor (Ln³⁺) have been evaluated at 77 K. The results suggest ET from the triplet state of naphthalene using an exchange mechanism. The ground state geometries of the system L and its complexes with Li⁺, Cs⁺ and Tb³⁺ have been determined using DFT methods to interpret our results.     

Effect of iodine doping on the electrical transport mechanism in plasma polymerized 2,6-diethylaniline thin films

The current density–voltage characteristics of pure and iodine doped plasma polymerized 2,6-diethylaniline (PPDEA) thin films of different thicknesses ranging from 150 to 450 nm with aluminum (Al)/PPDEA/Al structure have been investigated at room temperature. The direct current electrical conductivity has showed a higher value due to iodine doping of PPDEA thin film. In contrast to pure PPDEA thin films where the most probable conduction mechanism is electrode limited Schottky type, Poole–Frenkel (PF) conduction mechanism is found to be operative in iodine doped PPDEA thin films. The PF conduction mechanism in iodine doped PPDEA thin films may have generated due to the charge transfer complex formation through donor type monomer and acceptor type iodine. The presence of charge transfer complex is confirmed by a new absorption shoulder/peak in ultraviolet–visible spectrum of iodine doped PPDEA thin film.     

Fluorescence quenching of 9-cyanoanthracene in presence of zinc tetraphenylporphyrin in a polar liquid medium

Steady-state and time-resolved techniques are used to study photoinduced electron and/or excitational energy transfer processes involved within a novel donor (zinc tetraphenylporphyrin)-acceptor (9-cyanoanthracene) system in a polar liquid medium (acetonitrile) at the ambient temperature (300 K). After photoexcitation of 9-cyanoanthracene, its fluorescence emission as well as lifetime are found to be quenched in presence of zinc tetraphenylporphyrin. The fluorescence quenching is ascribed to be due to the combined effect of electron transfer from zinc tetraphenylporphyrin to 9-cyanoanthracene and energy transfer (radiative as well as non-radiative) from 9-cyanoanthracene to zinc tetraphenylporphyrin. The highly exergonic values of Gibbs free energy change for both forward electron transfer reaction (−1.15 eV) and charge recombination reaction (−1.94 eV) indicate the possibilities of occurrences of these two processes in the Marcus inverted region. The fluorescence quenching rate due to photoinduced electron transfer reaction is found to be close to the diffusion-controlled limit within the present donor-acceptor system upon excitation of the acceptor molecules.     

Hydrogen indium vacancy complex VInH4 in n-type InP studied by positron-lifetime

Positron-lifetime experiments have been carried out on two undoped n-type liquid encapsulated Czochralski (LEC)-grown InP samples with different stoichiometric compositions in the temperature range 10-300 K. For temperatures below 120 K for P-rich InP and 100 K for In-rich InP, the positron average lifetime began to increase rapidly and then leveled off, which was associated with the charge state change of hydrogen indium vacancy complexes from (V_InH₄)⁺ to (V_InH₄)⁰. This phenomenon was more obvious in P-rich samples that have a higher concentration of V_InH₄. The transformation temperature of approximately 120 K suggests that the complex V_InH₄ is a donor defect and that the ionization energy is about 0.01 eV. The ionization of neutral V_InH₄ accounted for the decrease of the positron average lifetime when the sample was illuminated with a photon energy of 1.32 eV at 70 K. These results provide evidence for hydrogen complex defects in undoped LEC InP.     

Near band-edge luminescence of semi-insulating undoped gallium arsenide at high levels of excitation

The dependences of the maximum and the half-width of near band-edge photoluminescence of semi-insulating undoped-GaAs crystals at 77 K on the concentration of background acceptor impurities and the level of excitation in the range from 3×10²¹ to 6×10²² quantum/(cm² s) are investigated. The observed dependences are explained by formation of the density tails of states as a result of fluctuations of impurity concentration and participation of localized states of the donor impurity band in radiative transitions. Reduction of many-particle interaction at increasing of N can be connected with increasing of shielding of charge carriers by atoms of impurity.     

Interaction of nobiletin with human serum albumin studied using optical spectroscopy and molecular modeling methods

The binding of nobiletin to human serum albumin (HSA) was investigated by fluorescence, UV-vis, FT-IR, CD, and molecular modeling. Fluorescence data revealed the presence of a single class of binding site on HSA and its binding constants (K) at four different temperatures (289, 296, 303 and 310 K) were 4.054, 4.769, 5.646 and 7.044×10⁴ M⁻¹, respectively. The enthalpy change (ΔH⁰) and the entropy changes (ΔS⁰) were calculated to be 1.938 kJ mol⁻¹ and 155.195 J mol⁻¹ K⁻¹ according to the Van’t Hoff equation. The binding average distance, r, between the donor (HSA) and the acceptor (nobiletin) was evaluated and found to be 2.33 nm according to the Förster's theory of non-radiation energy transfer. Changes in the CD and FT-IR spectra were observed upon ligand binding along with a significant degree of tryptophan fluorescence quenching on complex formation. Computational mapping of the possible binding sites of nobiletin revealed the molecule to be bound in the large hydrophobic cavity of subdomain IIA.     

Charge transfer and adsorption energies in the iodine-Pt(1 1 1) interaction

The adsorption energies for iodine atom on the fcc, hcp, bridge, and atop sites of the Pt(1 1 1) surface were determined using ab initio DFT method in two different unit cells. A periodic slab model is used and the obtained energies are in agreement with the corresponding experimental values extrapolated at 0 K. The charge transfer is determined by the use of the Hirshfeld partitioning scheme, and the charge transfer values follow the adsorption energy trend for different sites of the Pt(1 1 1) surface. The results show that the plane-wave DFT approach correctly describes the adsorption of iodine on the Pt(1 1 1) surface and support the use of the Hirshfeld method in surface science problems.     

Radiative transitions of layered semiconductor GaS doped with P

Photoluminescence (PL) measurement has been made on P-doped p-GaS. The 2.35 and 2.12 eV emission bands are observed in the PL spectrum of P-doped sample at 77 K. The temperature dependence of full-width at half-maximum and the shape of the PL spectrum of the 2.12 eV emission band are characterized by the recombination mechanism of the configurational coordinate model. It is found that the 2.12 eV emission band is related to the complex center of vacancy and acceptor due to P atoms. It is found from the presence of the complex center that the P-doped samples include a high concentration of defects or defect complexes.     

A spectrophotometric and thermodynamic study of the charge-transfer complexes of iodine with nortriptyline and imipramine drugs in chloroform and dichloromethane solutions

The interaction of iodine as electron acceptor with nortriptyline and imipramine drugs as electron donors has been investigated spectrophotometrically at various temperatures in chloroform and dichloromethane solutions. The observed time dependence of the charge–transfer band and subsequent formation of in solution were related to the slow transformation of the initially formed iodine: drug outer complex to an inner electron donor–acceptor (EDA) complex, followed by fast reaction of the inner complex with iodine to form a triiodide ion. The pseudo-first-order rate constants and activation parameters for the transformation process were evaluated from the absorbance-time data. Stoichiometrices of the complexes were defined by the Job’s method of the continuos variation and obtaind 2: 1 for iodine: drug complexes. The formation constants and molar absorptivities were evaluated from the absorbance-mole ratio data. Thermodynamic parameters of the complexes have been determined from the temperature dependence of the stability constant by Van’t Hoff equation.     

Phosphorescence from an EDA complex with nitrobenzene as an electron donor

Excitation of the EDA complex formed between the donor, nitrobenzene, and the acceptor, boron trichloride, gives rise to a phosphorescence centered at 579 nm with a quantum yield of 2.3 ± 0.1 × 10^-3, which is assigned to the charge transfer triplet state of the complex. The formation constant of the complex was determined to be 50 ± 15 M^-1 at 77 K. Photochemical quantum yield data at room temperature for the photoreduction of nitrobenzene as the nitrobenzene-boron trichloride complex to nitrosobenzene indicates reactivity increasing with boron trichloride concentration. A comparison of the phosphorescence and electrochemical data for the 1:1 EDA complexes between nitrobenzene, benzophenone and pyridine and boron trichloride predicts that the oxidation potentials for nitrobenzene and benzophenone are +1.32 and +1.63 V vs. the saturated calomel electrode, respectively, and reflect the availability of a non-bonding electron pair for complexation.     

Magnetoelectric behavior in the complex CaMn7O12 perovskite

We report a magnetoelectric effect in the double perovskite CaMn₇O₁₂, that shows a complex magnetic behavior below 90 K with two magnetic phases coexisting (one ferrimagnetic and the other modulated). A second magnetic transition, associated with changes in the magnetic modulation and magnetic ordering coherence lengths of the two magnetic phases occurs at 50 K (T_N2). A detailed structural characterization of this compound, that we have carried out by means of high-resolution X-ray powder diffraction, reveals an anisotropic thermal expansion of its lattice parameters at 50 K (T_N2). In addition, our study of the complex permittivity of this sample as a function of temperature, frequency and magnetic field shows very interesting results below 90 K and specially below 50 K: the dielectric constant ε′_r that was decreasing continuously on cooling experiences an upturn, and even more, on application of a magnetic field it shows a moderate magnetoelectric response. We attribute such dielectric behavior to the formation of electric dipoles by magnetostriction in this charge and spin ordered system, that are sensible to the presence of an external magnetic field.     

Complexation of bis‐crown stilbene with alkali and alkaline‐earth metal cations. Ultrafast excited state dynamics of the stilbene‐viologen analogue charge transfer complex

The complex formation of bis(18‐crown‐6)stilbene ( 1 ) and its supramolecular donor‐acceptor complex with N,N′‐bis(ammonioethyl) 1,2‐di(4‐pyridyl)ethylene derivative ( 2 ) with alkali and alkaline‐earth metal perchlorates has been studied using absorption, steady‐state fluorescence, and femtosecond transient absorption spectroscopy. The formation of 1 ?Mⁿ⁺ and 1 ?(Mⁿ⁺)₂ complexes in acetonitrile was demonstrated. The weak long‐wavelength charge‐transfer absorption band of 1 · 2 completely vanishes upon complexation with metal cations because of disruption of the pseudocyclic structure. The spectroscopic and luminescence parameters, stability constants, and 2‐stage dissociation constants were calculated. The initial stage of a recoordination process was found in the excited complexes 1 ?M⁺ and 1 ?(M⁺)₂ (M = Li, Na). The pronounced fluorescence quenching of 1 · 2 is explained by very fast back electron transfer (τ_et = 0.397 ps). The structure of complex 1 · 2 was studied by X‐ray diffraction; stacked ( 1 · 2 )_m polymer in which the components were connected by hydrogen bonding and stacking was found in the crystal. These compounds can be considered as novel optical molecular sensors for alkali and alkaline‐earth metal cations.     

Fabrication of Semiconductor Polymer Membranes Combined with a Colored Charge Transfer Complexes Used in the Manufacture of Solar Cells as a Source of Alternative Energy

The main task of this article was to prepared of new pigment model in situ solar cells accordance to charge-transfer complexes of rhodamine C (RhC) donor as dye laser gain media with iodine (σ-acceptor) and chloranilic acid, CLA (π-acceptor). The synthesis stoichiometry of these complexes were of 1∶2 (donor∶acceptor) with general formulas [(RhC)]I·I₃ and [(RhC)(CLA)₂]. The discussed data of elemental analysis, conductivity measurements, FT-IR, UV-Vis spectroscopy and photometric titration data visualized the stoichiometry, formula and complexity of the complexes. The physicochemical and spectroscopic analyses obtained suggested that the electron transfer occurred through nitrogen atom in a tertiary amine -N(C₂H₅)₂ of RhC donor with acceptor. The synthesized solid complexes were under go to thermogravimetric analyses to investigate their thermal stability and decomposition steps. The molar conductance measurements revealed that RhC complexes have an electrolytic statement. The thermal stability of rhodamine C complexes was enhanced in comparable with RhC itself. The polymer membranes of poly-methyl methacrylate) (PMMA) combined with the RhC charge(transfer complexes in chloroform solvent have been prepared and characterized by (infrared & electronic) spectroscopy and scanning electron microscopy (SEM) morphological examination. The photo-stability properties of the RhC complexes have been investigated.     

A series of copper(I) complexes with electron donor/acceptor embedded ligands: Synthesis, photophysical and electroluminescent properties

In this paper, we report the synthesis of four diimine ligands incorporated with an electron donor/acceptor, as well as their corresponding Cu(I) complexes with bis(2-(diphenylphosphanyl)phenyl) ether as an ancillary ligand, resulting in four phosphorescent Cu(I) complexes. Their crystal structures as well as photophysical and thermal properties are discussed in detail. Experimental data and theoretical calculations confirm that electron donor moieties and limited conjugation system may self-restrict geometry relaxation in excited states, leading to narrowed and blue-shifted emission bands. On the other hand, electron acceptor moieties and large coplanar conjugation system are ineffective in restricting geometry relaxation, leading to broadened and red-shifted emission bands. However, the introduction of electron donors compromises thermal stability of Cu(I) complexes. We also explore one of the Cu(I) complexes as a dopant for electroluminescence application, and a maximum luminance of 680 cd/m² peaking at 620 nm is achieved.     

EPR investigations of synthetic manganese complexes as bio-mimics of the water oxidation complex in photosystem II

Research in the Swedish Consortium for Artificial Photosynthesis aims to construct a supramolecular system containing synthetically connected D (electron donor), S (photosensitizer), and A (electron acceptor) compartments. These are intended to carry out catalytic water oxidation on the donor side and catalytic hydrogen formation on the acceptor side, driven by light energy absorbed by the photosensitizer. In this minireview, we focus our attention on our spectroscopic and electrochemical studies of a series of manganese complexes partially mimicking the water-oxidizing manganese complex in the natural photosystem II (PSII), using ruthenium(II) tris(bypyridine) as the photosensitizer. The manganese complexes we discuss fall in three categories: monomeric manganese systems covalently linked to the ruthenium(II) tris(bypyridine) center, dimeric manganese complexes that are not covalently connected to ruthenium(II) tris(bypyridine) and dimeric manganese complexes covalently bound to a ruthenium(II) tris(bypyridine) center via an amide bound. The review focuses on the use of electron paramagnetic resonance spectroscopy in the studies of our manganese compounds.     

Enhanced Emission Induced by FRET from a Long-Lifetime, Low Quantum Yield Donor to a Long-Wavelength, High Quantum Yield Acceptor

We report observation of high quantum yield, long-lifetime fluorescence from a red dye BO-PRO-3 excited by resonance energy transfer (RET). The acceptor fluorescence was highly enhanced upon binding to the donor-labeled DNA. A ruthenium complex (Ru) was chosen as a donor in this system because of its long fluorescence lifetime. Both donor and acceptor were non-covalently bound to DNA. Emission from the donor-acceptor system (DA) at wavelengths exceeding 600 nm still preserves the long-lifetime component of the Ru donor, retaining average fluorescence lifetimes in the range of 30–50 ns. Despite the low quantum yield of the Ru donor in the absence of acceptor, its overall quantum yield of the DA pair was increased by energy transfer to the higher quantum yield acceptor BO-PRO-3. The wavelength-integrated intensity of donor and acceptor bound to DNA was many-fold greater than the intensity of the donor and acceptor separately bound to DNA. The origin of this effect is due to an efficient energy transfer from the donor, competing with non-radiative depopulation of the donor excited state. The distinctive features of DA complexes can be used in the development of a new class of engineered luminophores that display both long lifetime and long-wavelength emission. Similar DA complexes can be applied as proximity indicators, exhibiting strong fluorescence of adjacently located donors and acceptors over the relatively weak fluorescence of separated donors and acceptors.