Przemysław Krawczyk

Electronic and vibrational contributions to first hyperpolarizability of donor-acceptor-substituted azobenzene.

In this study we report on the electronic and vibrational (hyper)polarizabilities of donor-acceptor-substituted azobenzene. It is observed that both electronic and vibrational contributions to the electric dipole first hyperpolarizability of investigated photoactive molecule substantially depend on the conformation. The contributions to the nuclear relaxation first hyperpolarizability are found to be quite important in the case of two considered isomers (cis and trans). Although the double-harmonic term is found to be the largest in terms of magnitude, it is shown that the total value of the nuclear relaxation contribution to vibrational first hyperpolarizability is a result of subtle interplay of higher-order contributions. As a part of the study, we also assess the performance of long-range-corrected density functional theory in determining vibrational contributions to electric dipole (hyper)polarizabilities. In most cases, the applied long-range-corrected exchange-correlation potentials amend the drawbacks of their conventional counterparts.

DFT study of linear and nonlinear optical properties of donor-acceptor substituted stilbenes, azobenzenes and benzilideneanilines

A theoretical analysis of the linear and nonlinear optical properties of six push–pull π-conjugated molecules with stilbene, azobenzene and benzilideneaniline as a backbone is presented. The photophysical properties of the investigated systems were determined by using response functions combined with density functional theory (DFT). Several different exchange-correlation potentials were applied in order to determine parameters describing the one- and two-photon spectra of the studied molecules. In particular, the recently proposed Coulomb-attenuated model (CAM-B3LYP) was used to describe charge-transfer (CT) excited states. In order to compare theoretical predictions with available experimental data, calculations with inclusion of solvent effects were performed. The BLYP and the CAM-B3LYP functionals were found to yield values of two-photon absorption (TPA) probabilities closer to experimental values than the B3LYP functional or the HF wavefunction. Moreover, molecular static hyperpolarisabilities were determined using both DFT and second-order Møller-Plesset perturbation (MP2) theory. Likewise, the CAM-B3LYP functional was found to outperform other applied exchange-correlation potentials in determining first hyperpolarisability (β). Moreover, it was confirmed on a purely theoretical basis that the presence of a –C=C– bridge between the phenyl rings leads to a much larger nonlinear optical response in comparison with a –N=N– bridge.

Theoretical study of one- and two-photon absorption spectra of azoaromatic compounds

In this study, the one- and two-photon absorption spectra of seven azoaromatic compounds (five pseudostilbenes-type and two aminoazobenzenes) were theoretically investigated using the density functional theory combined with the response functions formalism. The equilibrium molecular structure of each compound was obtained at three different levels of theory: Hartree-Fock, density functional theory (DFT), and Møller-Plesset 2. The effect of solvent on the equilibrium structure and the electronic transitions of the compounds were investigated using the polarizable continuum model. For the one-photon absorption, the allowed pi-->pi(*) transition energy showed to be dependent on the molecular structures and the effect of solvent, while the n-->pi(*) and pi-->pi(*)(n) transition energies exhibited only a slight dependence. An inversion between the bands corresponding to the pi-->pi(*) and n-->pi(*) states due to the effect of solvent was observed for the pseudostilbene-type compounds. To characterize the allowed two-photon absorption transitions for azoaromatic compounds, the response functions formalism combined with DFT using the hybrid B3LYP and PBE0 functionals and the long-range corrected CAM-B3LYP functional was employed. The theoretical results support the previous findings based on the three-state model. The model takes into account the ground and two electronic excited states and has already been used to describe and interpret the two-photon absorption spectrum of azoaromatic compounds. The highest energy two-photon allowed transition for the pseudostilbene-type compounds shows to be more effectively affected (approximately 20%) by the torsion of the molecular structure than the lowest allowed transition (approximately 10%). In order to elucidate the effect of the solvent on the two-photon absorption spectra, the lowest allowed two-photon transition (dipolar transition) for each compound was analyzed using a two-state approximation and the polarizable continuum model. The results obtained reveal that the effect of solvent increases drastically the two-photon cross-section of the dipolar transition of the pseudostilbene-type compounds. In general, the features of both one- and two-photon absorption spectra of the azoaromatic compounds are well reproduced by the theoretical calculations.

Synthesis and Linear and Nonlinear Optical Properties of Three Push–Pull Oxazol-5(4H)-one Compounds

Three uncharged push-pull oxazol-5(4H)-ones were synthesized and thoroughly characterized. The examined molecules contained electron-donor and electron-acceptor groups interacting via a π-conjugated bridge. Spectral properties of the oxazol-5(4H)-ones were studied in detail in three solvents of different polarities. The results indicate a solvatochromic shift toward lower energy for the charge-transfer state. The compounds are weakly fluorescent in polar solvents, but they have high fluorescence quantum yields in nonpolar solvents. Their two-photon absorption (2PA) properties were characterized by the open- and closed-aperture Z-scan technique, by the pump-probe technique, and by the two-photon excited fluorescence method. The dyes exhibit relatively high effective two-photon absorption cross sections ranging from 490 to 2600 GM at ~100 GW/cm(2), according to the Z-scan results, which are found, however, to contain significant contribution from higher-order absorption processes. In addition, these compounds display good photostability.

Linear and nonlinear optical properties of azobenzene derivatives

The results of computations of spectroscopic parameters of lowest–lying electronic excited states of azobenezene derivatives are presented. The analysis of experimentally recorded spectra was supported by quantum chemical calculations using density functional theory. The theoretically determined resonant (two-photon absorption probabilities) and non-resonant (first-order hyperpolarisability) nonlinear optical properties are also discussed, with an eye towards the performance of recently proposed long-range corrected (LRC) schemes (LC–BLYP and CAM–B3LYP functionals).

Time-dependent density functional theory calculations of the solvatochromism of some azo sulfonamide fluorochromes.

The absorption and emission spectra of three azo sulfonamide compounds in different solvents were investigated theoretically by using response functions combined with density functional theory (DFT), while the solvent effect on the structure and the electronic transitions was determined using the integral equation formalism for the polarizable continuum model (IEF-PCM). The results show that the applied different exchange-correlation functionals can reproduce the experimental values well. DFT calculations of the title compounds showed that the H-bond formed between the solute and solvent molecules is one of the major causes of the reversible solvatochromism observed in measured spectra. This is due to a better stabilization of the neutral form than the zwitterionic form in the polar protic solvents, which is characteristic of the hypsochromic shift. On the other hand, the molecules considered exhibit a monotonic behavior regarding the polarity of the low-lying excited state (Δμg–CT) as a function of the solvent polarity. This dependence occurs in the case of the positive solvatochromism and confirms the thesis regarding the H-bond solute–solvent interactions. Theoretically determined values of the two-photon cross section revealed that the (σOF(2)) shows similar trends with changes in λabs, in contrast to 〈δOF〉 values. In conclusion, the results demonstrate that the investigated molecules can be used successfully as fluorochromes in bioimaging.

Spectroscopic and nonlinear optical properties of new chalcone fluorescent probes for bioimaging applications: a theoretical and experimental study

AbstractIn this study, the newly synthesized non-centrosymmetric, 4-dimethylamino-3′-isothiocyanatochalcone (PKA) compound was presented. This compound belongs to the chalcone group, and its main purpose is to be used in biomedical imaging as a fluorescence dye. For this reason, the linear and nonlinear properties in solvents of different polarity were thoroughly studied. In accordance with the requirements for a fluorochrome, the PKA compound is characterized by strong absorption, large Stokes’ shifts, relatively high fluorescence quantum yields and high nonlinear optical response. Moreover, the isothiocyanate reactive probe was conjugated with Concanavalin A. Conventional fluorescence microscopy imaging of Candida albicans cells incubated with the PKA-Concanavalin A, is presented. The results of this study show that the novel conjugate PKA-Concanavalin A could be a promising new probe for cellular labelling in biological and biomedical research. Graphical abstractSpectroscopic behavior of the PKA dye

Experimental and theoretical studies of the influence of solvent polarity on the spectral properties of two push-pull oxazol-5-(4H)-one compounds

Spectral and photophysical properties of two derivatives of the 2-phenyl-1,3-oxazol-5(4H)-ones were studied in 17 solvents of different polarity. These compounds have either push-pull non-centrosymmetric or C3-symmetric structures with electron-withdrawing groups (2-phenyl-oxazolone) introduced onto the triphenylamine. It has been found that their spectral and photophysical properties depend on the structure of the compounds and on the solvent polarity. The non-radiative relaxation process is facilitated by an increase of the solvent polarity. The changes in the electronic absorption and fluorescence maximum positions with solvent polarity were analyzed applying different solvent polarity parameters based on Lippert-Mataga, McRae, Bakhshiev and Kawski theories or ETN scale. The long-wavelength absorption band positions exhibit a slight dependence on the solvent, whereas the fluorescence spectra demonstrate substantial positive solvatochromism. It was found that the position of the electronic absorption band depends mainly on the solute polarizability (related to the solvent refraction index function f(n2)=(n2-1)/(2n2+1)), whereas the solvent polarity influences the position of the fluorescence band. Quantum chemical calculations of the transition energies and dipole moments at the DFT level have been also performed. The difference between the first excited and ground state dipole moments was found experimentally to be 10.8 D and 13.0 D according to Bakhshievs model. The experimental values of Δμ were compared to that one obtained from theoretical calculations for various solvents.