Martins Rutkis

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 of the compounds revealed increased steric bulk and conformational freedom of the triphenylsilyl moiety. While the presence of the triphenylsilyl group results in more stable glasses and increased material nonlinearity, in the case of trityl groups, measured glass transition temperatures are higher.

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 been recorded for tret-butyl substituted DMABI chromophore.

Effect of Corona Poling and Thermo Cycling Sequence on NLO Properties of The Guest-Host System

In the case of doped polymer system SHG efficiency is proportional to the concentration and orientation degree of NLO-active molecules. Unfortunately, corona poling realised at elevated temperatures causes concentration decrease of NLO-active molecules due to crystallization. On the basis of our studies of the film optical images, refractive index and SHG measurements of the dimethylaminobenzylidene 1,3-indandione and PMMA guest-host system, we have demonstrated that optical quality is improved and second order NLO efficiency is higher, when the external poling electric field is switched on from the very beginning of the sample heating process.

Structure–property relationship of isomeric diphenylethenyl-disubstituted dimethoxycarbazoles

Isomeric 3,6-dimethoxy- and 2,7-dimethoxycarbazoles containing diphenylethenyl moieties were synthesized by condensation of the appropriate dimethoxycarbazoles with diphenylacetaldehyde. The solid-state structures and the molecular order of the compounds were proven by X-ray crystallography. Both compounds were found to be capable of glass formation with comparable glass transition temperatures (70–71 °C). They exhibited high thermal stabilities, with the 5% weight loss temperatures exceeding 375 °C. The isomer having diphenylethenyl groups at C-3 and C-6 positions and methoxy groups at C-2 and C-7 positions (3a) exhibited aggregation-induced emission (AIE), while its counterpart having diphenylethenyl groups at C-2 and C-7 positions and methoxy groups at C-3 and C-6 positions (3b) showed the opposite effect, i.e. aggregation-caused quenching (ACQ). The derivative 3b showed superior charge transporting properties. Time-of-flight hole drift mobilities in its layers approached 10−3 cm2 V−1 s−1 at high electric fields. A comparative theoretical analysis of the compounds was performed using density functional theory (DFT) and time-dependent DFT calculations. They proved more effective π-conjugation in the derivative of 3,6-dimethoxy carbazole (3b), which was also observed by UV and fluorescence spectroscopies. The theoretical study revealed relatively low ground state dipole moment of 0.69 D of the isomer 3b, while its counterpart (3a) showed much higher ground state dipole moment of 5.98 D. The difference in polarity was found to have the crucial effect on the molecular arrangement in the crystals and consequently, on the thermal transitions and charge-transporting properties.

Reversible trans/cis photoisomerization in Langmuir-Blodgett multilayers from polyfunctional azobenzenes

Abstract Four novel, amphiphilic, N -acylaminoazobenzene derivatives containing a sulfonyl group and a β-alanine moiety were synthesized and their mono- and multilayers were prepared by the Langmuir-Blodgett (LB) technique. The opto-physical properties of the LB multilayers were investigated. Some relationship between the chemical structure of the azobenzenes and photosensitivity of their LB multilayers has been found. Reversible trans/cis photoisomerization was observed on alternate irradiation with ultraviolet and visible light of LB multilayers from azobenzenes modified by the introduction of a second aliphatic chain in the N -acylamino fragment as well as by introduction of the bulky N,N′ -dicyclohexyl urea moiety.

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 temperature values of 76–134 °C. The nonlinear optical (NLO) properties of these compounds were characterized using quantum chemical calculations and second harmonic generation (SHG) measurements in corona-poled thin glassy films. The twisted geometry of the CICA based materials was shown to be beneficial to the macroscopic NLO performance due to the less pronounced solid phase stacking compared to the flat IDCA based compounds. The presence of site isolating groups at both the acceptor and donor ends of the molecule in compound 13 resulted in a considerable NLO efficiency increase. Non-centrosymmetric crystals of CICA based N,N-dimethylaminobenzylidene 7b were obtained and showed a SHG response comparable to urea.

Influence of corona poling procedures on linear and non-linear optical properties of polymer materials containing indandione derivatives as a cromophores

SHG efficiency of the poled guest - host polymer system is proportional to the concentration and orientation degree of NLO active molecules (chromophores). Corona poling realized at elevated temperatures could cause concentration decrease of NLO- active molecules due to centrosymmetric crystallization. Our studies showed that number density of crystallites is depending on orientation procedure. To obtain the best orientation procedure for guest - host systems containing four different chromophores based on dimethylaminobenzylidene 1, 3 - indandione we have compared optical images and SHG efficiency of corona poled films. According to our observations external poling electric field applied from the very beginning of the sample heating process can reduce crystallite grow. The optical quality is improved and SHG efficiency in some cases is up to 1.6 (depending on molecule structure) times larger after our suggested orientation sequence compared to classic corona poling procedures.

Photochromism of Some Azobenzene Derivatives in Thin Films as a Function of the Chemical Properties of the Molecule

Abstract The effect of the modification of the structure of azobenzene molecule by introduction a variety of functional groups on the photoisomerization in Langmuir-Blodgett and vacuum evaporated films has been investigated. The switching effect of the absorption, the surface potential and the electrical properties in thin layers of compounds has been discussed. A novel approach to the design of azobenzene amphiphiles, such as introduction of large bulky substituents in the molecule providing for a free volume necessary for the trans-to-cis photoisomerization, gave a number of valuable photochromic materials for investigation of reversible optically induced switching processes.

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 emission maxima is in range from 570 nm to 710 nm. Incorporation of bulky trityloxy ethyl groups combining with existing tert-butyl groups results in thin solid films formation of synthesized glasses from volatile organic solvents (chloroform, dichloromethane) without them being doped in any polymer. This makes them perspective for potential applications in organic light-emitting diodes and organic lasers by simple luminescent layer composition with cheap wet-casting approaches. All glasses show good thermal stability with thermal decomposition temperatures from 264° to 318°C and glass transition values up to 158°C for DWK-1TB. These thermal properties of synthesized glasses could make them also useful for potential applications in other optical materials such as materials for nonlinear optics.

Simple method for measuring bilayer system optical parameters

A simple method for measuring bilayer system refractive indexes and thicknesses in the low absorbing part of spectra is demonstrated. The method is based on application of Savitzky - Golay smoothing filters and interference fringe separation in the reflected or transmitted spectra of the bilayer system. The refractive indexes and thicknesses are extracted from the wavelengths corresponding to extreme points in the spectrum. Due to the fact that wavelength difference of extreme points in the analyzed spectrum is defined by the product of both, the layer thickness and refractive index, one must generate an appropriate initial guess of these parameters. For refractive index approximation two different methods have been used - point by point and Sellmeier dispersion relation. The final optimization procedure is based on a priori assumption that the thickness calculated from permutations of all extreme points in the spectrum should be the same. Thus the optimal penalty parameter for finding the solution is the standard deviation of calculated thicknesses. In order to demonstrate the effectiveness of this simple method, results of thin organic film thicknesses and refractive indexes are presented.