0000000000082638
AUTHOR
Andrejs Tokmakovs
Triphenyl moieties as building blocks for obtaining molecular glasses with nonlinear optical activity
The incorporation of trityl and triphenylsilyl groups into low molecular weight molecules allows the formation of stable molecular glasses. A series of materials based on the N-phenyldiethanolamine core was synthesized bearing different azobenzenes and benzylydene-1,3-indandione as active chromophores. Molecular hyperpolarizability of the synthesized compounds was calculated by a restricted Hartree–Fock method with basis 6-31G(d,p) and measured in solutions by hyper-Rayleigh scattering. Non-linear optical (NLO) activity of the thin glassy films was confirmed after a corona poling procedure. Thermal sustainability of the NLO response of up to 85 °C was achieved. Quantum chemical calculations…
Optical properties of the low-molecular amorphous azochromophores and their application in holography
The films based on the low-molecular amorphous azochromophore 2-(3-(4-((4- (Ethyl(2-(trityloxy)ethyl)amino)phenyl)diazenyl)styryl)-5,5-dimethylcyclohex-2-enylidene) malononitrile (IWK-2M) were prepared. The optical properties of the material, such as transmittance and reflection spectra of the film, sensitivity to polarization holographic recording by two wavelengths (405 and 532 nm) were studied. The direct relief formation during the polarization holographic recording was explored, relief depth dependence on exposure and record beam intensity was investigated. The holographic matrix on this material base was produced without chemical etching process; the replication of holographic image w…
All-organic electro-optic waveguide modulator comprising SU-8 and nonlinear optical polymer
Institute of Solid State Physics, University of Latvia (SJZ/2016/26); Ministry of Education and Science, Republic of Latvia (MultIfunctional Materials and composItes, photonicS and nanotechnology (IMIS2)). We acknowledge Dr. Anatolijs Sarakovskis at Institute of Solid State Physics for the XPS measurements.
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…
Optical phase retrieval using four rotated versions of a single binary mask – simulation results
In signal processing one often faces the phase problem, i.e., when an image is formed information about the phase is lost so that only information about intensity is available. This is often an issue in astronomy, biology, crystallography, speckle imaging, diffractive imaging where the phase of the object must be known. While there have been many approaches how to find a solution to the phase problem, numerical algorithms recovering the phase from intensity measurements become more and more popular. One of such algorithms called PhaseLift has been recently proposed. In this study, we show that even 4 masks may be sufficient for reasonable recovery of the phase. The original wavefront and th…
Modular approach to obtaining organic glasses from low-molecular weight dyes using 1,1,1-triphenylpentane auxiliary groups: Nonlinear optical properties
Abstract A new modular synthetic approach to obtain organic glasses from low-molecular weight azobenzenes and stilbenes has been accomplished using 1,1,1-triphenylpentane crystallization preventing auxiliary groups. Six new structures show excellent solubility in non-polar solvents and thin films with good optical qualities have been obtained using a spin-coating technique. The glass transition temperatures of the new amorphous materials were in the range of 73–108 °C. The nonlinear optical activity in thin amorphous films was measured after a corona poling procedure.
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.
The effect of noise, a constant background, and bit depth on the phase retrieval of pure phase objects
Acknowledgements – The authors are supported by the postdoctoral project (1.1.1.2/16/I/001; 1.1.1.2/ VIAA/1/16/199, State Education Development Agency, Republic of Latvia).
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…
Stereoselective synthesis and properties of 1,3-bis(dicyanomethylidene)indane-5-carboxylic acid acceptor fragment containing nonlinear optical chromophores
A series of organic push–pull type chromophores using indane-1,3-dione 5-carboxylic acid (IDCA) and novel 1,3-bis(dicyanomethylidene)indane 5-carboxylic acid (CICA) electron acceptor fragments have been synthesized and characterized. NMR and X-ray analysis revealed that condensation reactions with the CICA fragment were stereoselective and yielded benzylidenes and azomethines with E double bond configurations. Due to the non-planar geometry these compounds are chiral and were acquired as a racemic mixture. The subsequent functionalization of the carboxylic acid group with 5,5,5-triphenylpentan-1-ol yielded solution-processable glass forming materials (6, 8, 10, 13) with glass transition tem…
Nanocrystalline CaWO$_4$ and ZnWO$_4$ Tungstates for Hybrid Organic-Inorganic X-ray Detectors
The experiment at the DESY PETRA-III synchrotron was performed within project No. I-20211105 EC at the Institute of Solid State Physics, University of Latvia, as the Cen ter of Excellence has received funding from the European Union’s Horizon 2020 Framework Pro gramme H2020-WIDESPREAD-01-2016-2017-TeamingPhase2 under grant agreement No. 739508, project CAMART2.
Triphenyl group containing molecular glasses of azobenzene for photonic applications
Abstract D-π-A type organic molecules have attracted considerable attention of scientists due to their potential applications in nonlinear optics and holographic data storage as light, flexible and low-cost photonic materials. To provide a better understanding on the relation between the compound chemical structure and their physical properties necessary for the mentioned purposes, eight glassy triphenyl group containing derivatives of azobenzene with incorporated 5,5-dimethylcyclohex-2-enylidene or 4H-pyran-4-ylidene structural fragments and dicyanomethylene, indene-1,3-dione and pyrimidine-2,4,6(1H,3H,5H)-trione acceptor groups have been synthesized and investigated. Thermal stability of …
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 …
All-Organic Waveguide Sensor for Volatile Solvent Sensing
This work was supported by ERDF 1.1.1.1 Activity Project Nr. 1.1.1.1/16/A/046 “Application assessment of novel organic materials by prototyping of photonic devices”. We acknowledge Igors MIHAILOVS for valuable discussions.
Structure-dependent tuning of electro-optic and thermoplastic properties in triphenyl groups containing molecular glasses
Abstract The series of seven molecular compounds composed of D–π–A chromophores and triphenylmethyl auxiliary groups were characterized by UV–Vis spectroscopy, differential scanning calorimetry and quantum chemical calculations. Nonlinear optical (NLO) properties of compounds were determined by second harmonic generation measurements in corona poled thin glassy films. The results show that triphenylmethyl auxiliary groups are effective at shielding undesirable dipole interactions in solid phase thus increasing NLO efficiency of materials. Thermal stability up to 108 °C was achieved for a polar order in poled samples.
An improved molecular design of obtaining NLO active molecular glasses using triphenyl moieties as amorphous phase formation enhancers
New molecular design of obtaining molecular glasses has been developed by linking triphenylmethyl moieties to chromophore core by flexible C-C bridge. Compounds capable of forming stable amorphous phase with good optical quality have been acquired with increased chemical and thermal sustainability compared to the previously reported design. NLO activity of compounds has been measured after corona discharge polling. Compared to previously synthesized trityloxy fragment containing compounds increase of d 33 coefficient by up to 17 times was achieved for the same chromophore core containing compounds.
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…
Wavefront Recovery: Shack-Hartmann Aberrometry vs PhaseLift Using a Single Binary Amplitude Modulating Mask
We investigate whether a wavefront can be recovered by using a single mask rotated in four different positions. Results show that PhaseLift can recover the wavefront from intensity measurements using such a kind of modulation.
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.
Optical phase retrieval using four rotated versions of a single binary amplitude modulating mask
In recent years, phase retrieval methods recovering the phase of an object from coded diffraction patterns have gained popularity. A numerical phase retrieval method called PhaseLift that recovers the phase of an object from a very limited number of coded diffraction patterns was recently proposed. Performance of PhaseLift has been analyzed for different types and the number of masks modulating an object. We present a unique application of PhaseLift that uses four rotations of a single mask, modulating only the amplitude of an object. In simulations, a phase screen with the root-mean-square (RMS) value 0.294 μm was used as the test object. The RMS value of the retrieved phase screen after …
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…
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
CCDC 1436954: Experimental Crystal Structure Determination
Related Article: Kaspars Traskovskis, Valdis Kokars, Andrejs Tokmakovs, Igors Mihailovs, Edgars Nitiss, Marina Petrova, Sergey Belyakov, Martins Rutkis|2016|J.Mater.Chem.C|4|5019|doi:10.1039/C6TC00203J