0000000000082639
AUTHOR
A. Jurgis
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…
Insight in NLO Polymer Material Behavior from Langevin Dynamic Modeling of Chromophore Poling
Calculation of chromophore polar order, i.e. the polarization of nonlinear optically (NLO) active polymers poled by external field, is challenging. One possible solution is to reproduce the orientation polarization of chromophores under external field using Langevin dynamics (LD) molecular modeling. The present work investigates the influence of chromophore dipole moment, density and field extent on NLO efficiency and polarization/relaxation dynamics. Results of simulations convince us, that the method is applicable for modeling real NLO polymers. In the spotlight of this investigation we would like to describe a NLO polymer as a “ferrofluid” where chromophores are active particles or elect…
Inspirations for EO polymer design gained from modeling of chromophore poling by Langevin dynamics
One of the possibilities to create organic molecular material for NLO applications are polymers with dispersed NLO active chromophores. These molecules must be acentrically ordered by applying an external electric poling field. The NLO efficiency depends on dipole moment, molecular hyperpolarizabilities, concentration of the chromophores and external poling field strength. Calculating, from first principles, the extent of the alignment and via this NLO efficiency has proven to be challenging. One approach to solve this problem is pure analytic statistical mechanics treatment, what could be enhanced by Monte Carlo ( MC ) statistical mechanical modelling. The chromophore molecules usually hav…
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.
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…