Dipolar NLO Chromophores Bearing Diazine Rings as π-Conjugated Linkers.

The synthesis of a series of push-pull derivatives bearing triphenylamine electron-donating group, cyclopenta[c]thiophen-4,6-dione electron acceptor and various π-linkers including (hetero)aromatic fragments is reported. All target chromophores with systematically varied π-linker structure were further investigated by electrochemistry, absorption measurements, and EFISH experiments in conjunction with DFT calculations. Based on electrochemical and photophysical measurements, when a polarizable 2,5-thienylene moiety is embedded into the chromophore π-backbone the highest intramolecular charge transfer (ICT) is observed. Benzene, pyrimidine, and pyridazine derivatives exhibit lower polarizability and extent of the ICT across these π-linkers. The elongation of the π-conjugated system via additional ethenylene linker results in a significant reduction of the HOMO-LUMO gap and an enhancement of the NLO response. Whereas it does not significantly influence electrochemical and linear optical properties, the orientation of the pyrimidine ring seems to be a key parameter on the µß value due to significant variation of the dipolar moment (µ) value. In 2a and 2c, pyrimidine is oriented to behave as an acceptor and thus generate dipolar molecule with µ above 5 D, whereas in 2b and 2d ground state dipole moment is significantly reduced. This study seems to indicate a high aromaticity of pyrimidine and pyridazine derivatives, close to the benzene analogues and significantly higher than thiophene analogues.

Light induced self-written waveguides interactions in photopolymer media.

We present experimental and theoretical study of the interaction of Light Induced Self-Written (LISW) waveguides in photopolymers. We show that the diffusion of the monomer controls the refractive index distribution. Consequently it influences the interaction between the LISW channels allowing the observation of anti-crossing behavior or the propagation of an array of non interacting LISW waveguides.

Solvent-free fluidic organic dye lasers.

We report on the demonstration of liquid organic dye lasers based on 9-(2-ethylhexyl)carbazole (EHCz), so-called liquid carbazole, doped with green- and red-emitting laser dyes. Both waveguide and Fabry-Perot type microcavity fluidic organic dye lasers were prepared by capillary action under solvent-free conditions. Cascade Förster-type energy transfer processes from liquid carbazole to laser dyes were employed to achieve color-variable amplified spontaneous emission and lasing. Overall, this study provides the first step towards the development of solvent-free fluidic organic semiconducting lasers and demonstrates a new kind of optoelectronic applications for liquid organic semiconductors.

Electro-optic phase modulation in light induced self-written waveguides propagated in a 5CB doped photopolymer.

We present the inscription of a Light Induced Self-Written (LISW) waveguide in a 4-cyano-4'-pentylbipheny (5CB) doped photopolymer. The dynamic reorientation of the 5CB molecules in the material under applied electric field leads to birefringence in LISW waveguide and thus allows the control of the phase of the guided mode.

Polarization state studies in second harmonic generation signals to trace atherosclerosis lesions.

We have performed multi-photon image reconstructions as well as polarization state analyses inside an artery wall affected by atherosclerosis to investigate the changes in collagen structure. Mice, either healthy or affected by spontaneous atherosclerosis, have been used for this purpose. A two-photon imaging system has been used to investigate atherosclerotic lesions in the ascending aorta of mice. Second harmonic imaging has been performed alternatively on healthy samples and on affected region. The reconstructed images show that the spatial distribution of the collagen network seems disorganized by the disease. The polarization state studies reveal however that the apparent disorganization of the collagen is related to its spatially diffuse distribution and that the internal structure of the collagen fibers is not affected by the disease. In addition, a theoretical simulation of the second harmonic polarization states shows that they are consistent with the known 3D structure of the collagen network.

Broadband transient dichroism spectroscopy in chiral molecules.

We perform time-resolved broadband transmission ellipsometry using the ultrafast pump-probe technique in an original setup. Our setup allows us to measure, over a wide spectral range, the optical rotary dispersion of the sample or, when needed, its circular dichroism by adding a broadband quarter-wave plate. While our experiment has been designed to study the transient states in chiral molecules, it performs sufficiently well to also characterize the ground state.

External stimulus driven variable-step grating in a nematic elastomer.

We report on the creation of micro-patterns in an oriented nematic elastomer (an artificial muscle material) by photopolymerization of surface aligned nematic liquid crystal monomers. We demonstrate that microscopic techniques are able to create accurate patterns in rubber-like liquid crystal materials. Two approaches, based on one and two-photon excitations respectively, are implemented using a microscope-based setup. Due to its high spatial selectivity, the two-photon excitation mode yields finer patterns. Benefitting from the intrinsic, thermally-induced, contractile properties of the material, gratings with variable steps in response to temperature changes were fabricated.

Refractive-index saturation-mediated multiple line emission in polymer thin-film distributed-feedback lasers.

We report experimental and theoretical investigations of multiple laser-line emission in a distributed-feedback dye laser pumped by two coherent optical beams. We have used a Lloyd interferometer configuration with second- and third-order Bragg reflections to study the interaction between the two incident pumps in an organic thin film. We demonstrated theoretically that the number of laser emission lines can be interpreted with reference to the saturation effect in the refractive index.

Rewritable optical data storage in azobenzene copolymers.

We propose to encode optical information through the localized depoling of polar chromophores in thin films of grafted polymeric materials with a femtosecond near IR laser source. This disorientation is promoted through the photoisomerization of the azo-dye component induced by a twophoton absorption process. We show that the resulting localized loss in second harmonic generation efficiency can be exploited in data storage applications. The low irradiation powers used allow for a recycling by reheating and repoling the films leading to a rewritable system.