0000000000246062
AUTHOR
Valdis Kampars
Dendronized azochromophores with aromatic and perfluoroaromatic fragments: Synthesis and properties demonstrating Ar ArF interactions
Abstract Syntheses of four new dendronized azochromophores were performed from 2-(2-amino-5-nitrophenoxy)ethanol, 2-[methyl(phenyl)amino]ethanol, 3,5-bis(benzyloxy)benzoic acid and 3,5-bis[(pentafluorophenyl)methoxy]benzoic acid using azo coupling reaction and ester formation reaction in presence of N,Nʹ-dicyclohexylcarbodiimide and 4-(dimethylamino)pyridine. Arene-perfluoroarene (Ar ArF) interactions are demonstrated in single crystal structure of dendronized azochromophore between pentafluorophenyl fragment and acceptor part of the azochromophore. The effect of Ar ArF interactions becomes apparent in thermal and nonlinear optical properties of the chromophores. Glass transition temperatur…
<title>Hologram recording in azobenzene oligomers</title>
Elementary hologram (holographic grating) recording and their coherent optical erasure have been experimentally studied in azobenzene oligomer (ABO) layers differing by their chemical composition, matrices and by the connection type of azobenzene chromophores to the matrix (dispersed or covalently bound). The best holographic parameters (7.9% diffraction efficiency and 86 J/cm2 specific recording energy) were achieved in the samples with covalent bonding to the matrix. Vector recording is also possible. Recording is unstable and reversible. The coherent optical erasure studies have shown its efficiency dependencies on the initial diffraction efficiency, erasing beam intensity and grating pe…
Novel azobenzene precursors for NLO active polyuretanes: Synthesis, quantum chemical and experimental characterization
Abstract For the development of electro optical active polyurethanes six new derivatives of 2-{(2-hydroxyethyl)-[4-(4-nitrophenylazo)phenyl]amino}ethanol and two of 2-{(2-hydroxyethyl)-[4-(5-nitropyridin-2-ylazo)phenyl]amino}ethanol were synthesized by azocoupling reaction. Molecular geometry, hyperpolarizability βFF and ground state dipole moment μg were acquired by RHF ab initio (6–31G∗∗) calculations using HyperChem software package. To characterize NLO performance of synthesized azo compounds second order non linear coefficients d31 and d33 were measured as function of chromophore load in guest–host films (PMMA). Eight synthesized compounds can be grouped in four similar gross formula p…
New Figure of Merit for Tailoring Optimal Structure of the Second Order NLO Chromophore for Guest-Host Polymers
Reliability to forecast SHG efficiency using two sets of non linear optical (NLO) chromophore figures of merit (FOM) was tested. One of them predicts that SHG efficiency d 33 of the poled guest-host polymer is proportional to ground state dipole ∼ μg, another to ∼ 1/μg. Correlation of maximal achieved second order NLO efficiency of the PMMA based systems containing eight dimethylaminobenzylidene-1, 3-indandione (DMABI) related chromophores with proposed FOM have been analyzed. The best correlations were obtained with second set of FOM, especially if high dipole moment (μg > 7D) chromophores are included in analysis.
Synthesis, optical, and thermal properties of glassy trityl group containing luminescent derivatives of 2-tert-butyl-6-methyl-4H-pyran-4-one
In this work we present simple preparation of original trityl group containing glassy luminescent 6-styryl substituted derivatives of 2-(2-tert-butyl-4H-pyran-4-ylidene)malononitrile (DWK-1TB), 2-(2-tert-butyl-4H-pyran-4-ylidene)-2- ethyl-2-cyanoacetate (KWK-1TB), 2-(2-tert-butyl-4H-pyran-4-ylidene)-1H-indene-1,3(2H)-dione (ZWK-1TB) and 5-(2-tert-butyl-4H-pyran-4-ylidene)pyrimidine-2,4,6(1H,3H,5H)-trione (JWK-1TB). Their optical properties have been investigated. The absorption maxima of synthesized glasses is in region from 425 nm to 515 nm and emission maxima is from 470 nm to 625 nm in solution of dichloromethane. But absorption maxima of their solid films is from 425 nm to 500 nm and em…
Holographic recording of surface relief gratings in tolyle-based azobenzene oligomers
Abstract Holographic recording of surface relief gratings (SRG) in tolyle-based azobenzene oligomer films have been carried out at 514.5 nm. It was experimentally studied by spectroscopic and AFM methods. The maximum surface modulation amplitude was 35 nm. SRG formation is explained by the mean-field model and by the photodegradation of chromophores enabling the directional mass transport as the result of trans–cis transformations. The conclusion is made that SRG are stable but the diffraction efficiency (DE) changes are due to the complementary decaying amplitude-phase gratings. Strong polarization dependences of transmitted and reflected DE are found. They are explained by the diffraction…
Thermal, glass-forming, nonlinear optical and holographic properties of "push-pull" type azochromophores with triphenyl moieties containing isophorene and pyranylidene fragments
Molecular organic compounds with electron donating fragment bounded through π-conjugated system with electron acceptor fragment, as well as with incorporated triphenyl groups in their molecules show potential for creating cheap and simple solution processable materials with nonlinear optical properties. Additional insertion of azobenzene fragment in their structures makes them also possible to form holographic volume and surface relief gratings (SRG) after exposure to laser radiation, which could be useful for holographic data storage. For these purposes polymers are generally used. However, their application is complicated and challenging task as in every attempt to obtain the same polymer…
Light induced processes in thin films of indandione type organic molecules
The optically induced switching of material properties is important for investigations of opto-electronic effects and optomechanical properties. Investigated organic materials contain chromophore dipole consisting of acceptor and donor groups bridged by a delocalized p-electron system. Both calculations and experimental data show a reversible highly dipolar photoinduced intra molecular charge transfer in indandione type molecules (DMABI) accompanied by change of the sign and the value of the dipole moment. Investigations of optical properties of thin host-guest polymer films show that the photoinduced process of DMABI is related to the photoinduced switching between two equally stable state…
Optimized Deposition of Graphene Oxide Langmuir-Blodgett Thin Films
Abstract Single sheet graphene (SG) is an innovative transparent material with high electrical and thermal conduction the use of which in transparent electrodes instead of traditional materials improves the performance of optoelectronic devices. In this study, graphene oxide (GO) has been obtained by a modified Hummer`s method followed by an advanced technique of water removal (lyophilisation). The Langmuir-Blodgett (LB) method was applied to transfer GO from suspension to substrate. To optimize the deposition process, as suspending and spreading solvents the benzene and benzene/methanol mixtures were chosen instead of previously studied water suspensions. The number of GO layers in suspens…
PV effect of fullerene/poly(3-hexylthiophene) blend sensitized by phthalocyanine having infrared absorption CT band
An attempt was made to extend the photosensitivity spectral range of fullerene/poly(3-hexylthiophene) blend to NIR region by adding extra electron donor — hydroxygallium phthalocyanine (GaOHPc) with a strong and wide intermolecular charge transfer (CT) band around 830 nm. Multilayer cells of ITO/PEDOT: PSS/6 GaOHPc/P3HT: C61(CO2Et)2 have been prepared by spin coating with vacuum evaporated Al or In top electrodes. Significant photosensitivity of the cells was in 370–900 nm spectral range. However charge carrier photogeneration efficiency was 3 times higher for illumination in P3HT absorption band as compared with the GaOHPc CT band at 830 nm. But when GaOHPc was mixed in the blend forming P…
Synthesis of azobenzene substituted tripod-shaped bi(p-phenylene)s. Adsorption on gold and CdS quantum-dots surfaces
We report here the synthesis of several tripod-shaped oligo(p-phenylene)s with legs composed of two phenylene units. Each leg is end-capped with a thioacetate group for adhesion to metallic surfaces. An azobenzene chromophore group is present on the functional arm of the tripod. The key step in the synthesis is the Pd-catalyzed Suzuki cross-coupling reaction of the silicon derivative core molecule with substituted phenyl moieties and azobenzene derivatives. Gold surfaces prepared by thermal evaporation and CdS quantum-dots surfaces were covered by the tripod-shaped molecules. Modified surfaces were characterized by atomic force microscopy (AFM), fluorescence, and Kelvin Probe analyses.
Holographic properties of azobenzene oligomers with differently bonded chromophore groups
Holographic properties of two types (I and II, specified in the text) of azobenzene oligomers (ABO) have been experimentally studied in the spectral region of low absorption at 633 nm. In the case of type I ABO the chromophore groups were covalently bonded to either tolyl-polyurethane or hexamethylene-polyurethane matrix. In the case of type II ABO azobenzene chromophores were dispersed in polystyrene matrix, and their concentration was varied from 0.005 to 0.200 mol/l. Samples were in the form of 10 µm thick films. In both cases the diffraction efficiency exposure time dependences were measured for the holographic grating period of 2 (m at 633 nm. The diffraction efficiency of more than 2%…
Hyper-Rayleigh scattering and two-photon luminescence of phenylamine- indandione chromophores
Based on results of quantum chemical (QC) screening, we put under research several phenylamine indane-1,3-dione derivatives including octupolar NLO chromophore A3BI. According to these calculations, molecular first hyperpolarizability (βHRS) should be enhanced upon replacement of methyl substituents with phenyl groups. Surprisingly, βHRS values obtained in our measurements by hyper-Rayleigh scattering (HRS) are much higher than one could expect from QC. Bearing in mind that two-photon luminescence (TPL) is usual cause for overestimation of βHRS in HRS measurements, we have accomplished investigations of TPL properties of these compounds. All investigated triphenylamine derivatives exhibit s…
Rational computing of energy levels for organic electronics: the case of 2-benzylidene-1,3-indandiones
Device engineering in organic electronics, an active area of research, requires knowledge of the energy levels of organic materials (traditionally but ambiguously denoted as HOMO and LUMO). These can be effectively determined by electrochemical investigation, but yet more effective would be quantum chemical (QC) computation of these quantities. However, there is no consensus on the computational method in the research community. Ongoing discussions often focus on choosing the right density functional method, but neglect other model parameters, in particular, the basis set. This study considers comparison of various methodologies and parameters for predicting ionization energy I and electron…
Nonlinear optical properties of low molecular organic glasses formed by triphenyl modified chromophores
The series of organic molecular glasses have been studied as possible candidates for nonlinear optical (NLO) applications. Amorphous phase formation of investigated materials is ensured by the presence of bulky triphenyl substituents in molecular structure of NLO chromophores. Linear optical properties as well as NLO coefficients and thermal stability of NLO activity for the 13 molecular materials in glassy thin solid films have been determined. For the benzylidene-1,3-indandione chromophore containing compound the highest d33 value equal to 280 pm/V was measured under the 1064 nm excitation. Among the investigated compounds uppermost achieved thermal sustainability of NLO response was 108 …
Toward device applicable second order NLO polymer materials: definition of the chromophore figure of merit
Maximal achieved second order non linear optical (NLO) efficiency of the PMMA based host – guest systems containing eight dimethylaminobenzylidene -1, 3 - indandione (DMABI) related chromophores have been analysed. Two contradicting sets of NLO chromophore figure of merit (FOM) equations were tested. One of them predicts that NLO efficiency of the poled polymer host -guest film is proportional to ground state dipole d33 ~ 1/μg, another to d33 ~ 1/μg. The best correlations for the maximal achieved nonlinearity were obtained with second set of FOM, especially if high ground state dipole (μg > 7D) chromofores are included in analysis.
Indanedione based binary chromophore supramolecular systems as a NLO active polymer composites
Novel route to obtain EO material is proposed by supramolecular assembly of neutral-ground-state (NGS) and zwitterionic (ZWI) NLO chromophores in binary chromophore organic glass (BCOG) host–guest system. On a basis of our Langeven Dynamics (LD) molecular modeling combined with quantum chemical calculations, we have shown that anticipated enhancement NLO efficiency of BCOG material is possible via electrostatic supramolecular assembly of NGS with ZWI chromophore in antiparallel manner. Binding energy of such complex could be more dependent on molecular compatibility of components and local (atomic) charge distribution, then overall molecular dipole moments. According to our LD simulations t…
Synthesis and nonlinear optical properties of novel N,N-dihydroxyethyl-based molecular organic glasses using triaryl substitutes as amorphous phase formation enhancers
In given study a new structural design of molecular NLO materials is presented where amorphous phase formation is achieved by introduction of bulky trityl and triphenylsilyl substituents. Obtained materials formed stable organic glasses with good optical quality and glass transition temperatures notably exceeding ambient. NLO activity was successfully measured in samples that underwent corona discharge poling. The comparison of both enhancer groups revealed, that trityl group increases thermal sustainability of material, while triphenylsilyl group better promotes formation and stability of amorphous phase.
Novel second-order nonlinear optical polymer materials containing indandione derivativatives as a chromophore
Second order non linear optical (NLO) properties of sPMMA based host-guest systems containing eight dimethylaminobenzylidene -1, 3 - indandione (DMABI) related chromophores have been investigated by means of quantum chemical calculations and SHG experimental characterization. Ab initio calculations with basis set 6-31G were used for molecular geometry determination as well as in the calculations of molecular hyperpolarizability by FF approach. Influence of the chromophore concentration on the host-guest film NLO performance was obtained by SHG Maker fringe experiments. The highest value of d53233 =80 pm/V (frequency corrected value d033 =12 pm/V) at chromophore concentration 15 %wt have bee…
Polymers films with indandione derivatives as alternatives to azobenzene polymers for optical patterning
Surface relief gratings (SRGs) on organic thin films are studied extensively for both scientific interest and in relevance to the applications. Among the chromophores being used the azobenzenes showed the best performance, but the use of alternative photo-sensitive groups provides better general understanding of the phenomena. A thermodynamic theory and molecular dynamics simulations of photoinduced effects are discussed. In this study we use indandione derivatives, known as promising materials for photonics applications, as an alternative to the azobenzenes. We consider their photoreactions when incorporated into a polymer film. One of interesting features is the spectral dependence of the…
Structure optimization of azobenzene oligomers for holography
Azobenzene oligomer layers with side chain chromofore groups (ChG) has been experimentally studied to optimize scalar and vector hologram recording at 633 nm. ChG with different acceptors (Br, NO2, H, CN) and different bonding type to the matrix (dispersed without bonding or with covalent bonding) were used. The influence of oligomer matrix (polyvinylbuthirol, tolyle, hexamethylene, polyvinylpirolidone, double matrix) and spacers was also studied. The best results (the maximal diffraction efficiency of 7.9% and the minimal specific recording energy of 0.38 J/(cm2 %)) are obtained for ChG with one NO2 acceptor group covalently bonded to tolyle matrix. Double matrix considerably decreases the…
CCDC 1520858: Experimental Crystal Structure Determination
Related Article: Lauma Laipniece, Valdis Kampars, Sergey Belyakov, Andrejs Tokmakovs, Edgars Nitiss, Martins Rutkis|2019|Dyes Pigm.|162|394|doi:10.1016/j.dyepig.2018.10.035