Observation of second-harmonic generation in an oriented glassy nematic phase of a closo-decaborane derivative

The optical second-harmonic generation(SHG) and the linear optical properties were investigated in a planar cell containing aligned nonchiral nematic derivative of B₁₀H₁₀²⁻: 1-(4-heptyloxypyridin-1-yl)-10-(4-pentyl-1-thiacyclohexyl)-closo-decaborane (HPTD) as a function of temperature. The compound showed a low level of the SHG signal in the polycrystalline state, and no nonlinear optical effect was detected in the fluid nematic state (N) either in the presence or absence of an orienting electric field. When frozen, the resulting thermodynamically unstable nematic glassy phase (glassyN) unexpectedly exhibited the second-order nonlinear optical properties, implying a partial polar order in the arrangement of the in-plane-aligned molecules in a liquid-crystal cell. The efficiency of the SHG was analyzed for two polarization configurations yielding the main component of the second-order nonlinear susceptibility χₓₓₓ(²)=2.3±0.3pmV⁻¹ along the nematic director x. A comparison of the experimental susceptibility with a hypothetical one estimated from the vectorial component of the molecular hyperpolarizability showed a relatively low degree of the spontaneous polar order. The dispersion of the principal refractive indices in the glassy state of HPTD was derived from dichroic absorption spectra using an interference fringe method and fitted with a Sellmeier-type equation. At 527nm the birefringence of HPTD is Δn=0.31.The authors acknowledge the Australian Research Council Discovery Project No. DP0556942 and the NSF Grant No. DMR-0111657 for financial support

Deoxyribonucleic acid-based photochromic material for fast dynamic holography

The authors report on a biopolymeric material made of deoxyribonucleic acid (DNA) complexed with the cationic surfactant cetyltrimethyl-ammonium (CTMA) and doped with the photochromic disperse red 1 dye (DR1) for dynamic holographic recording. The molar ratio of the DNA-CTMA to the dye is about 5:1. They have found that the photochromic properties of DR1 in the DNA-CTMA matrix are favorably modified in speed of response with respect to conventional polymeric matrices. Dynamic holographic gratings which were inscribed in DR1:DNA-CTMA films are characterized by switching times within a 1–10ms range. An excellent reversibility of the recording process is reported.The authors acknowledge the Australian Research Council Discovery Project No. DP0556942, the Materials and Manufacturing Directorate Air Force Office of Scientific Research, the AOARD Grant No. 05-4010, and the Polish Ministry of Science and Higher Education Grant No. N50713231/3302 for financial support

Ab initio studies of two-photon absorption of some stilbenoid chromophores

Two-photon absorption of a series of donor-acceptor trans-stilbene derivatives is studied by means of density functional theory applied to second-order response function. Several important issues in modeling are highlighted which must be addressed for a reliable reproduction of the experimental results. It is evident that the correct order of magnitude of calculated two-photon absorption cross sections can only be obtained if proper account is taken of vibrational broadening of the absorption profiles. A comparison of the theoretical results with the experimental ones indicates that the computed two-photon absorption cross sections are in rough agreement with our previous report, although the observed systematic increase of the cross sections with the electron acceptor strength is not well reproduced. It is suggested that this disagreement may be due not only to the deficiencies of the computations but also to a variety of factors contributing to the experimental value of the effective two-photon absorption cross section, which are not taken into account in the ab initio calculations

Charge carrier mobility in an organic-inorganic hybrid nanocomposite

Organic-inorganic hybrid materials are media for electronic and optoelectronic applications. We present a study of the electronic transport in such a modelnanoparticle-sensitizedhybridorganic-inorganic photorefractive host system, consisting of poly(N-vinylcarbazole) doped with quantum dots of cadmium sulfide, using standard time-of-flight techniques. The photocurrent transients exhibit features typical of dispersive transport in an amorphous semiconductor. The hole mobility depends strongly on the electric field and temperature indicating Poole–Frenkel-like activated hopping transport; a thickness dependence of the mobility is observed. The presence of nanoparticles does not lead to increased trapping of holes. Conversely, a surprising result is observed: the mobility actually increases with the increase of nanoparticle concentration even though it is well below the percolation limit.This study was supported by a NSF, DMR Solid State and Polymer Chemistry Grant No. DMR0075867. Partial support by a Defense Research Initiative on Nanotechnology (DURINT), Contract No. F496200110358, through the Directorate of Chemistry and Life Sciences of the Air Force Office of Scientific Research is also acknowledged

Asymmetric properties between the forward and backward stimulated emission generated by ultrafast three- and four-photon excitation

This paper presents the observation of asymmetric behavior between the forward and backward stimulated emission, generated in multiphoton active dye solutions, through three- or four-photon excitation of subpicosecond laser pulses. At a pump energy level considerably higher than the lasing threshold value, the peak wavelengths of the forward stimulated emission are 20–30-nm shorter than those of the backward stimulated emission for the two investigated stilbazolium dye solutions (PRL-L3 and PRL-L10). This obvious spectral asymmetry can be explained by the following three considerations: (i) the difference of spatial/temporal sequences between the forward and backward stimulated emission pulses; (ii) blueshift of the peak wavelength of transient gain experienced by the forward stimulated emission pulse; and (iii) saturation of reabsorption at the forward lasing wavelength range. These proposed explanations are verified by a specially designed pump-probe experiment, utilizing a white-light continuum as the probe beam and the ∼1300-nm laser radiation as the pump beam for three-photon excitation. The experimental results have clearly shown the existence of the saturation effect of reabsorption and the gain-peak blueshift effect as well as their transient features

Quadratic and Cubic Nonlinear Optical Properties of Salts of Diquat-Based Chromophores with Diphenylamino Substituents

A series of chromophoric salts has been prepared in which 4-(diphenylamino)phenyl (Dpap) electron donor groups are connected to electron-accepting diquaternized 2,2′-bipyridyl (diquat) units. The main aim is to combine large quadratic and cubic nonlinear optical (NLO) effects in potentially redox-switchable molecules with 2D structures. The chromophores have been characterized as their PF_6^− salts by using various techniques including electronic absorption spectroscopy and cyclic voltammetry. The visible absorption spectra are dominated by intense π → π* intramolecular charge-transfer (ICT) bands, and all of the compounds show two reversible or quasireversible diquat-based reductions and partially reversible Dpap oxidations. Single crystal X-ray structures have been obtained for one salt and for the precursor compound (E)-4-(diphenylamino)cinnamaldehyde, both of which adopt centrosymmetric space groups. First hyperpolarizabilities β have been measured by using hyper-Rayleigh scattering (HRS) with a 800 nm laser, and Stark (electroabsorption) spectroscopy of the ICT bands affords estimated static first hyperpolarizabilities β_0. The directly and indirectly derived β values are large and generally increased substantially for the bis-Dpap derivatives when compared with their monosubstituted analogues. Polarized HRS studies show that the NLO responses of the disubstituted species are dominated by “off-diagonal” β_(zyy) components. Lengthening the diquaternizing alkyl unit lowers the electron-acceptor strength and therefore increases the ICT energies and decreases the E_(1/2) values for diquat reduction. However, compensating increases in the ICT intensity prevent significant decreases in the Stark-based β_0 responses. Cubic NLO properties have been measured by using the Z-scan technique over a wavelength range of 520−1600 nm, revealing relatively high two-photon absorption cross-sections of up to 730 GM at 620 nm for one of the disubstituted chromophores

Nonlinear dynamics of two-color optical vortices in lithium niobate crystals

We study experimentally the nonlinear dynamics of two-color optical vortex beams in the presence of second-harmonic generation combined with the effects of photo- and thermal refraction, as well as self- and induced-phase modulation.We use an iron-doped lithium niobate crystal as a nonlinear medium for the vortex propagation and observe experimentally, depending on the laser wavelength, a decay of a double-charge vortex, splitting and reshaping of background beam, pattern formation, and controllable nonlinear rotation of a vortex pair

DNA-Ormocer based biocomposite for fabrication of photonic structures

We report microfabrication of high quality photonicstructures such as two-dimensional photonic crystals and beam splitters from a high DNA load, photosensitive Ormocer nanocomposite. This nanocomposite combines the high dye loading capacity of DNA with the photopatternability and hardness of the Ormocer. The fabrication is performed with the two-photon lithography method. Detailed studies of the deoxyribonucleic acid distribution in the fabricatedstructures are conducted with Raman microscopy. We also demonstrate that the deoxyribonucleic acid based nanocomposite films cast on glass substrates are of high enough quality to support amplified spontaneous emission from dyes intercalated in the deoxyribonucleic acid

Synthesis and optical power limiting properties of heteroleptic Mo3S7 clusters

Substitution of the halide ligands in (Bu4N)2[Mo3S7X6] (X = Cl, Br) by diimine ligands, such as 4,4′-dimethyl-2,2′-bipyridine (dmbpy), 2,2′-bipyridine (bpy) and 1,10-phenanthroline (phen), affords the neutral heteroleptic clusters Mo3S7Cl4(dmbpy) (1), Mo3S7Br4(dmbpy) (2), Mo3S7Br4(bpy) (3), and Mo3S7Br4(phen) (4). Further substitution of the halide ligands in Mo3S7Br4(diimine) clusters by dmit (1,3-dithiole-2-thione-4,5-dithiolate) allows the preparation of the mixed diimine–dithiolene neutral cluster complexes Mo3S7(dnbpy)(dmit)2 (5, dnbpy = 4,4′-dinonyl-2,2′-bipyridine), Mo3S7(dcmbpy)(dmit)2 (6, dcmbpy = 4,4′-dimethoxycarbonyl-2,2′-bipyridine), and Mo3S7(dcbpy)(dmit)2 (7, dcbpy = 2,2′-bipyridine-4,4′-dicarboxylic acid). The optical limiting properties of complexes 1–7 have been assessed by the open-aperture Z-scan technique at 570 nm, employing a nanosecond optical parametric oscillator. In order to investigate the effect of increasing the π-system, complexes 1–4, with the general formula Mo3S7X4(diimine), (X = Cl, Br), were compared to clusters 5–7, containing the dmit ligand. The influence of the metal content on the optical power limiting properties was also investigated by comparing the trinuclear series of complexes prepared herein with the bis(dithiolene) dinuclear cluster (Et4N)2[Mo2O2S2(BPyDTS2)2], which has been recently prepared by our group. All trinuclear clusters 1–7 are efficient optical limiters (σeff > σ0) with the threshold limiting fluence F15% decreasing on proceeding from dinuclear to trinuclear clusters and, generally, on extending the π-system.Financial support from the Spanish Ministerio de Economia y Competitividad (MINECO) (Grant CTQ2011-23157), UJI (research project P1.1B2013-19) and Generalitat Valenciana (Prometeo/2014/022 and ACOMP/2014/274) is gratefully acknowledged. The authors also thank Serveis Centrals d ’ Instrumentació Cientifica (SCIC), within Universitat Jaume, I for providing them with materials characterization facilities. D. R. thanks the Spanish Ministerio de Economía y Competividad for a predoctoral fellowship. M. G. H. thanks the Australian Research Council for support. M. S. acknowl- edges the NCN grant DEC-2013/10/A/ST4/0011