On the spectral properties of methyl and methoxy derivatives of 1,3-diphenyl-1H-pyrazolo[3,4-b]quinoxalines: Experiment and DFT/TDDFT calculations.

Paper reports the synthesis and spectroscopic studies of two novel 1,3-diphenyl pyrazoloquinoxaline (PQX) derivatives with 6-substituted methyl (MePQX) or methoxy (MeOPQX) side groups. The optical absorption and fluorescence emission spectra are recorded in solvents of different polarity. Other photophysical constants, such as the fluorescence lifetime and quantum yield, radiationless and radiative rate constants, electronic transition dipole moments, give complete characterization of MePQX and MeOPQX dyes as materials for potential luminescence or electroluminescence applications. Measured optical absorption and fluorescence emission spectra are compared with the results of quantum-chemical analysis using density functional theory (DFT/TDDFT) methods based on hybrid and long range corrected (LRC) exchange-correlation (xc) functionals in combination with solvation self consistent reaction field model. Comparing to conventional hybrid xc-functionals, the DFT/TDDFT calculations using LRC xc-functionals yield considerably more accurate description of optical absorption and fluorescence emission spectra. The best description of the absorption-emission circle provides the model assuming that optical absorption takes place from preferably flat or weakly twisted molecular conformations in the ground state, as particularly is suggested by the geometrical DFT optimization, whereas the fluorescence emission would be expected from more twisted molecular conformations in the excited state.

Spectral kinetics of fluorescence spectra of fluoroderivatives of pyrazoloquinoline in different polymer matrices.

Three fluoro-substituted pyrazoloquinoline derivatives have been placed in polymer matrices: polycarbonate, poly(methyl methacrylate) and polystyrene. Absorption, excitation and time-resolved fluorescence spectra have been recorded and luminescence lifetime of the optically active composites has been determined. Influence of the dielectric environment the optical properties of the chromophores are discussed. Experimental data and conclusions are supported with (TD)DFT calculations.

IR laser induced spectral kinetics of AgGaGe3Se8:Cu chalcogenide crystals.

The possibility to operate by optical spectra near the absorption edge gap was discovered for the AgGaGe3Se8:Cu semiconducting chalcogenide crystals under influence of microsecond CO2 laser with pulse energy 60 mJ operating at wavelength 10.6 µm. An occurrence of substantial photoinduced optical density was observed at wavelengths in the spectral range of 610-620 nm. Introducing of Cu ions leads to substantial spectral asymmetry in the observed spectra. The process achieves its maximum value after the 80-120 s of CO2 laser treatment and relaxes with almost irreversible changes after the same time. The contribution of thermo heating did not exceed 5-6%. Only the irreversible changes of the sample's surface topography were observed during the CO2 laser treatment, which do not influence the treatment. So the surface states do not play a principal role and the effect is prevailingly originated from the. The observed effect may be used for control of the CO2 laser power density.

Novel dipyrazolopyridine derivatives as deep blue emitters for polymer based organic light emitting diodes.

Paper reports synthesis and spectroscopic properties of four newly synthesized dipyrazolo[3,4-b; 3',4'-e]pyridine (DPP) derivatives. The spectroscopic studies are supplemented by quantum-chemical calculations using DFT/TDDFT/PCM method at the B3LYP/6-31+G(d,p) level of theory. The optical absorption and fluorescence emission processes appear to be weakly dependent on attached side phenyl and/or methyl groups exhibiting in cyclohexane solution the first absorption band (00' transition) in the region of 386-401 nm and the fluorescence band (0'0 transition) in the range of 412-425 nm. The electroluminescence devices (OLEDs) with an active PVK layer doped by DPP dyes have been designed. All the devices exhibit deep blue electroluminescence with the emission maximum being rather weakly dependent on the type of the fluorescent dopant. The obtained results demonstrate that a series of newly synthesized DPP dyes may be considered as perspective blue fluorescent emitters for electroluminescent applications.

Optical operation by chromophores featuring 4,5-dicyanoimidazole embedded within poly(methyl methacrylate) matrices.

We have studied photoinduced absorption, birefringence, and optical second-harmonic generation in poly(methyl methacrylate) (PMMA) films doped by organic chromophores featuring 4,5-dicyanoimidazole in the weight content equal to 5%. The chromophores indicated as IM1-IM6 were synthesized from 2-bromo-1-methylimidazole-4,5-dicarbonitrile by either nucleophilic substitution or Suzuki-Miyaura cross-coupling reaction. The samples were obtained as films of several micrometers thickness by the spin-coating method on a quartz substrate. Measurements of the optically induced birefringence were done by the Senarmont method at wavelength 1150 nm, and photoinduced absorption was studied in the spectral range 250-700 nm under optical treatment by 300 mW cw 532 nm laser. Photoinduced optical effects were studied by bicolor 1064 and 532 nm coherent laser pulses. The maximal changes were observed for the ratio between fundamental and writing beam intensities equal to about 7:1. To interpret the observed experimental measurements, theoretical simulations of photoinduced optical properties were performed by quantum chemical computational methods.

Spectroscopy of fluoro derivatives of 1H-pyrazolo[3,4-b]quinoline in different solvents.

Theoretical simulations of UV-vis spectra for organic chromophores: 3-(4-fluorophenyl)-1,4-diphenyl-, 1-(4-fluorophenyl)-3,4-diphenyl- and 4-(4-fluorophenyl)-1,3-diphenyl-1H-pyrazolo[3,4-b]quinoline. Density Functional Theory 6-31G calculations were performed. The molecular geometry and UV-vis spectra were simulated with the time-dependent DFT calculations. Influence of number of occupied and excited states on the behavior of the spectra is explored. To further improve the calculations a Polarizable Continuum Model (PCM) was employed to simulate the influence of solvent polarity. It was used in both geometry optimization and spectra simulation. An attempt to find a correlation between the values of dipole moments and the spectral shifts was performed. The results were compared with experiment.

Influence of chromophore dipole moments in parameters of organic light emitting devices based on phenyl and methyl modified pyrazoloquinoline.

Absorption, photo- and electroluminescence spectra of some trityl substituted 1H-pyrazolo[3,4-b]quinolines derivatives (methyl- and phenyl substituted) and fabrication of the single layered organic light emitting diodes are reported. The bulky trityl substituent was introduced to prevent aggregation and crystallization of the dopant in polymer matrix. Role of ground state dipole moments in the observed red Stokes shift, electroluminescent features and photocarrier transport is explored. The maximally achieved brightness about 50Cd/m(2) is observed in the spectral range extending from 443nm up to 462nm. The voltage threshold was varied from 7.8V up to 10V. The brightness-current dependences show an existence of at least two types of carrier injections.

Optical absorption of bisphenol A based pyrazoloquinoline dimers.

The paper presents the measured absorption spectra for several newly synthesized derivatives of bisphenol A based pyrazoloquinoline dimers (BAPQD). The experimental results are compared with quantum chemical calculations performed by semiempirical method AM1 and PM3. Molecular mechanic analysis shows that BAPQD dyes possess by a large number of equilibrium molecular conformations with similar total energies and small energy barriers between these states; thus at room temperature (T=300 K) the molecular dynamics exhibits slow temporal evolution passing a large number of intermediate slightly non-equilibrium conformational states. For this reason the semiempirical quantum chemical methods have been combined with the molecular dynamics simulations. The semiempirical PM3 method exhibits the best agreement with the experimental data, especially in the prediction of the spectral position of the first absorption band (absorption threshold). Taking into account that such good agreement is found for a set of more complex organic systems like BAPQD this may be of substantial interest for chemical engineering which deals with the designing of new efficient organic luminophores for electroluminescent applications.

Spectral emission properties of 4-aryloxy-3-methyl-1-phenyl-1H-pyrazolo[3,4-b]quinolines.

Spectral emission properties of novel 4-aryloxy-1H-pyrazolo[3,4-b]quinolines were investigated. All of the compounds exhibit strong blue luminescence in the solution and in the solid state as well. Pyrazoloquinolines were used as dopants in PVK matrices in electroluminescent devices with ITO/PVK:PQ/Ca/Al light emitting diode configuration.

Photoluminescence of 1-phenyl,3-methyl pyrazoloquinoline derivatives.

Paper presents the absorption and photoluminescence of 7-TFM, 6-F, 6-CN, 6-TBu and 6-COOEt derivatives of 1-phenyl-3-methyl-1H-Pyrazolo[3,4-b]quinoline (MPPQ). The measured spectra are compared with the results of the quantum chemical calculations performed by means of the semi-empirical methods (AM1 or PM3) that have been applied either to the equilibrium molecular conformations in vacuo (T=0K) or combined with the MD simulations (T=300 K). The photoluminescent spectra of MPPQ dyes are highly solvatochromic. The emission bands broaden and shift to the red with the increasing of solvent polarity, indicating thus a substantial dipole moment of the excited states. According to the quantum chemical analysis the reason for the strong solvatochromism of MPPQ dyes is related with intramolecular charge transfer (ICT) state. Due to the large dipole moment in the twisted geometry the ICT state is believed to become the lowest excited state in a strongly polar environment. This would explain a considerable solvatochromic shift in the highly polar solvents observed for all MPPQ dyes in the experiment. Such hypothesis is supported by the semi-empirical quantum chemical evaluations.

Molecular dynamics modeling in quantum chemical calculations. Optical absorption spectra of 1,3-Dimethyl-1H-Pyrazolo[3,4-b]quinoline derivatives.

Paper presents the quantum chemical modeling of the optical absorption spectra of 6-fluoro, 6-bromo, 7-trifluoromethyl, 6-cyano and 6-carboethoxy derivatives of 1,3-Dimethyl-1H-Pyrazolo[3,4-b]quinoline. The calculations are performed by means of the semiempirical quantum chemical methods (AM1 or PM3) in combination with molecular dynamics (MD) simulations at T=300 K. It is shown that a particular rotational dynamics of the methyl, trifluoromethyl or ethyl groups practically does not influence the optical absorption in the spectral range 200-500 nm whereas broadening of absorption bands may be well reproduced within MD simulations including all types of nuclei vibrations. The results of calculations are compared with the measured spectra of optical absorption. The quantum chemical method AM1 in combination with MD simulations gives for all dyes the best agreement between the calculated and measured spectral positions of the first absorption band (absorption threshold).

Photoluminescence and electroluminescence of methoxy and carboethoxy derivatives of 1,3-diphenyl-1H-pyrazolo[3,4-b]quinoline.

A series of methoxy (MO) and carboethoxy (CE) derivatives of 1,3-diphenyl-1H-pyrazolo[3,4-b]quinoline ([DPPQ]) are characterized by spectroscopic methods. All dyes show the photoluminescent spectra which are highly solvatochromic. In the case of 6MO[DPPQ] and 6CE[DPPQ] the emission bands are broad and shifted to the red with increasing of solvent polarity whereas the dyes 6MO1pMO[DPPQ] and 6MO13pMO[DPPQ] exhibit a reverse solvatochromism. The large difference between the excited- and state-dipole moments indicates a strong electron transfer effects in all dyes. The EL spectra are obtained for the fabricated OLEDs with a general structure of EL device ITO/PVK:6X[DPPQ]/Ca/Al. The blue emission originating from PVK host matrix appears to be quenched in EL spectra of doped PVK matrix giving rise to emission in blue, blue-green or green spectral regions. The obtained results demonstrate that a series of newly synthesized methoxy and carboethoxy [DPPQ]-derivatives may be considered as promising materials for electroluminescent applications.

Photovoltaic response and values of state dipole moments in single-layered pyrazoloquinoline/polymer composites.

We report the photovoltaic response of composite films formed by polymer transport matrices poly(3-octylthiophene) (P3OT) and poly(3-decylthiophene) (PDT) with incorporated 1H-pyrazolo[3,4-b]quinoline (PAQ) chromophore (see the first figure). The photovoltage (PV) data were obtained for different substituted PAQ possessing different state dipole moments. The photovoltaic cells were formed between ITO and aluminum electrodes. We found that the PV signal of polymer/PAQ substantially depends on the state dipole moments of the pyrazoloquinoline chromophore. This fact indicates on a possibility of significant enhancement of PV efficiency by appropriate variations of the state dipole moments of chromophore. This results in photoinduced electron transfer from polymer serving as donors to PAQ being the electron acceptor. Despite an efficiency of the PV devices is below 1%, however, it may be substantially enhanced in future varying the chromophore state dipole moments appropriately.

Photoinduced transparency in polypyrrole films.

For the first time we have discovered drastic photoinduced effects in the transparency for the pyrrole films. Photoinduced investigations of transparency were performed for the polypyrroles with different number of the pyrrole rings. We have established a considerable increase of the transparency from 70-75% up to 82-84% for the wavelengths of the probing lasers operating within the 530-1040 nm spectral range. The photoexcitation was performed by nanosecond pulsed polarized Nd-YAG laser generating at 1.34 microm. The phototransparent changes are completely reversible and disappear after switching off the laser treatment. The typical relaxation time for the photoinduced transparency is equal to about 10-20 micros and the changes of the transparency are strictly related with the values of state dipole moments of the polypyrroles. As a possible mechanism for explanation of the observed dependences one can consider existence of the charged trapping levels intra the forbidden energy gaps which effectively interact with the electric strength of the external polarized optical field and state dipole moments of the particular polymers.

Spectroscopy of PVK-phenyl derivatives disturbed the long-range ordering of liquid crystalline phase.

It has been shown that replacing of O-CH3 substituents in PVK-phenyl derivative chromophores by C-N groups leads to appearance of long-ranged dipole-dipole interactions in the composites including PVK-CN, fullerenes and cyano-biphenyl derivatives. Following quantum chemical calculations it has been demonstrated that interaction of the chromophores with the LC matrices favors dipole-dipole ordering, however it description requires to take into account non-homogenous space charge density distribution. During doping by PVK-CN derivatives phase transition has been found from uniaxial system with pure nematic to the quasi-smectic LC state with the substantially different parameter of ordering. Moreover it was established that during this substitution the switching times drastically jump from millisecond to microsecond regime.

Optical absorption of methoxy and carboethoxy derivatives of 1,3-diphenyl-1H-pyrazolo[3,4-b]quinoline.

Paper deals with experimental investigations and quantum chemical calculations of the optical absorption spectra of methoxy and carboethoxy 1,3-diphenyl derivatives of the pyrazoloquinoline ([PQ]): 6-methoxy-1,3-dyphenil-[PQ], 6-methoxy-1,3-(p-methoxyphenyl)-[PQ], 6-methoxy-1-(p-methoxyphenyl)-[PQ] and 6-carboethoxy-1,3-diphenyl-[PQ]. The quantum chemical calculations are performed by means of the semiempirical quantum chemical methods (AM1 or PM3) applied to: (a) the equilibrium molecular conformation in vacuo (T=0 K); (b) the molecular dynamic (MD) trajectory (T=300 K) which includes the dynamics of a certain molecular fragment (moiety) only (fragmental MD simulations); or (c) the MD trajectory obtained for most general case within the total MD simulations at T=300 K. The results of these calculations are compared with the measured spectra of the optical absorption. The quantum chemical simulations show that the dynamics of the methoxy or carboethoxy groups practically does not influence the absorption spectrum whereas the strongest its modification (300

Influence of bond lengths between substituents and mother molecule on spectral properties of pyrazoloquinolines.

Absorption and luminescent spectra of several new synthesized pyrazolo-quinoline possessing different substituents are studied. Absorption spectra of all the considered compounds possess five relatively strong absorption bands at about 430, 320, 270, 253 and about 230 nm. A correlation between the bond lengths between the substituent molecule and mother molecule with the observed spectral shifts was found. Theoretical spectra obtained within semi-empirical quantum chemical AM1 calculation methods seem to be more widened compared to the experimental ones due to electron-vibration interactions. However generally a good coincidence between spectral positions between experimental and calculated spectral peak positions was achieved. The corresponding experimental spectra have an absorption edges situated at about 430 nm which appears in fairly good agreement with quantum chemical simulations, namely for absorption spectra calculated by semi-empirical AM1-method. The red shifts in the experimental luminescence spectra are a consequence of electron-vibration interactions which increase with the effective radius and polarizabilities of the particular substituents.

Specific features of UV-vis absorption spectra of cis- and trans-polythiophenes.

UV-vis optical spectra of several polythiophene with number of dimers n=1, 5, 10, 15 for cis- and trans-forms were investigated. The study was done theoretically using semi-empirical AM1 (Austin Model 1) and PM3 (Parametric Method 3) methods with the appropriate molecular geometry optimization. The experimental UV-vis absorption spectra were used for verification of the both semi-empirical theoretical models. With the increasing number of dimers a red shift of the absorption edge was observed. Solvent does not play a crucial role on behavior of the absorption spectrum. A comparison of the both semi-empirical methods with the observed experimental absorption spectra is performed. Role of state dipole moments of the investigated polythiophenes in the behavior of the observed UV-vis spectra is discussed. Particular role of pi-conjugated bonds is demonstrated.

Optical spectra of some 6-styrylo-1H-pyrazolo[3,4-b]quinolines.

It was proposed a method of synthesis several 6-styrylo1-1H-pyrazolo[3,4-b]quinolines as promising material for optoelectronics. Particularly, 6-styryl-1,3-diphenyl-1H-pyrazolo[3,4-b]quinolines were prepared by Wadsworth-Emmons reaction. One of advantageous of these materials is stability of their optical spectra versus the possible cis- and trans-transformation. Theoretical and experimental studies of optical absorption and photoluminescence excitation spectra for styryloquinolines were done. They show that the AM1 semi-empirical method gives better results compared to other approaches. We have found that the solvents do not play a role in the behavior of the spectra. The backside-substituted groups do not influence substantially the observed optical spectra.

Optical poling effect and optical absorption of cyan, ethylcarboxyl and tert-buthyl derivatives of 1H-pyrazolo[3,4-b]quinoline: experiment and quantum-chemical simulations.

We present here results of experimental studies and quantum-chemical simulations of optical absorption and optical poling effects performed on a new synthesized cyan, ethylcarboxyl and tert-buthyl derivatives of 1H-pyrazolo[3,4-b]quinoline incorporated into polymer matrix or dissolved in organic solutions. The efficiency of second-order optical susceptibility d vs photoinduced power density I(p) clearly saturates to certain magnitude d(eff) at sufficient power densities (I(p) > or = 1.3 GW cm(-2)). Comparing experimental data and results of semiempirical quantum-chemical simulations one can conclude that there exists generally a good correlation between the magnitude of saturated susceptibilities d(eff) and macroscopic hyperpolarizabilities for all compounds except the chromophore 1,3-dimethyl-6-cyano-[PQ] only. The discrepancy for this compound may reflect a specific contribution of surrounding polymer matrix. According to the quantum chemical analysis the methyl-containing cyan and ethylocarcoxyl derivatives reveal four/five strong absorption bands in the spectral range 200-500 nm. A substitution of the methyl groups by the phenyl group causes the substantial changes of the absorption spectra mainly in the spectral range 240-370 nm. Measured and calculated absorption spectra manifest rather good agreement mainly in the part regarding the spectral positions of the first oscillator (absorption threshold). The quantum-chemical PM3 method shows the best agreement with experiment. At the same time a considerable broadening almost of all absorption bands appears as a characteristic feature of all measured spectra. The discrepancies between the calculated and the measured spectra are attributed to electron-vibronic coupling as well as to a specific rotational dynamics of phenyl rings.