Role of the acceptor in tuning the properties of metal [M(II) = Ni, Pd, Pt] dithiolato/dithione (donor/acceptor) second-order nonlinear chromophores: combined experimental and theoretical studies.

The mixed-ligand complexes [M(II)(Et2dazdt)(mnt)] (M = Ni, 1; Pd, 2; Pt, 3) [Et2dazdt = N,N'-diethyl-perhydrodiazepine-2,3-dithione; mnt = maleonitrile-2,3-dithiolate] have been prepared and fully characterized. X-ray diffractometric studies on 1-3 (the structure of 1 was already known) show that the crystals are isostructural (triclinic, P-1), and two independent molecular entities are present in the unit cell. These entities differ in the orientation of the ethyl substituents with respect to the epta-atomic ring. In the C2S2MS2C2 dithiolene core the four sulfur atoms define a square-planar coordination environment of the metal where the M-S bond distances involving the two ligands are similar, while the C-S bond distances in the C2S2 units exhibit a significant difference in Et2dazdt (dithione) and mnt (dithiolato) ligands. 1-3 show in the visible region one or two moderately strong absorption peaks, having ligand-to-ligand charge-transfer (CT) character with some contribution of the metal, and show negative solvatochromism and molecular quadratic optical nonlinearity, which was determined by the EFISH (electric-field-induced second-harmonic generation) technique. These complexes are redox active and show two reversible reduction waves and one irreversible oxidation wave. Theoretical calculations based on DFT and TD-DFT calculations on complexes 1-3 as well as on [Pt(Bz2pipdt)(mnt)] (4) and [Pt(Bz2pipdt)(dmit)] (5) highlight the factors which affect the optical properties of these second-order redox-active NLO chromophores. Actually, the torsion angle of the dithione system (δ2) inversely correlates either with the oscillator strengths of the main transition of the complexes or with their beta values. The high beta value of 5 can be attributed both to its lowest torsion angles and to the extent of the π system of its dithiolate ligand, dmit.

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.

Combined experimental and theoretical study on redox-active d8 metal dithione-dithiolato complexes showing molecular second-order nonlinear optical activity.

Synthesis, characterization, NLO properties, and theoretical studies of the mixed-ligand dithiolene complexes of the nickel triad [M(II)(Bz(2)pipdt)(mnt)] (Bz(2)pipdt = 1,4-dibenzyl-piperazine-3,2-dithione, mnt = maleonitriledithiolato, M(II) = Ni, 1, Pd, 2, Pt, 3) are reported. Molecular structural characterization of 1-3 points out that four sulfur atoms are in a slightly distorted square-planar geometry. While the M-S bond distances are only slightly different, comparison of the C-C and C-S bonds in the C(2)S(2)MS(2)C(2) core allows us to point out a significant difference between the C-C and the C-S distances in Bz(2)pipdt and mnt. These findings suggest assigning a dithiolato character to mnt (pull ligand) and a dithione one (push ligand) to Bz(2)pipdt. Cyclic voltammetry of 1-3 exhibits two reversible reduction waves and a broad irreversible oxidation wave. These complexes are characterized in the visible region by a peak of moderately strong intensity, which undergoes negative solvatochromism. The molecular quadratic optical nonlinearities were determined by the EFISH technique, which provided the following values µß(λ) (10(-48) esu) = -1436 (1), -1450 (2), and -1950 (3) converted in µß(0) (10(-48) esu) = -463 (1), -684 (2), and -822 (3), showing that these complexes exhibit large negative second-order polarizabilities whose values depend on the metal, being highest for the Pt compound. DFT and TD-DFT calculations on 1-3 allow us to correlate geometries and electronic structures. Moreover, the first molecular hyperpolarizabilities have been calculated, and the results obtained support that the most appealing candidate as a second-order NLO chromophore is the platinum compound. This is due to (i) the most extensive mixture of the dithione/metal/dithiolato orbitals, (ii) the influence of the electric field of the solvent on the frontier orbitals that maximizes the difference in dipole moments between the excited and the ground state, and (iii) the largest oscillator strength in the platinum case vs nickel and palladium ones.

Redox-switchable chromophores based on metal (Ni, Pd, Pt) mixed-ligand dithiolene complexes showing molecular second-order nonlinear-optical activity.

The synthesis and full characterization of the redox-active nickel triad mixed-ligand dithiolene complexes based on Bz(2)pipdt = 1,4-dibenzylpiperazine-3,2-dithione and dmit = 2-thioxo-1,3-dithiole-4,5-dithiolate ligands are reported. These complexes show a reversibly bleacheable solvatochromic peak and a remarkably high negative molecular first hyperpolarizability, whose values depend on the metal being highest for the platinum(II) compound.

Filamentation-free self-written waveguides in a photopolymerizable medium initiated by multimode optical fibers.

The inscription of light-induced self-written waveguides (LISW) with multimode optical fibers cannot be achieved by using coherent light because of the filamentation phenomena coming from the interferences among the different propagating modes. To suppress this filamentation, we have used two distinct strategies, an incoherent light writing technique and an "on the flow" writing process, to demonstrate the buildup of 1.5 mm long multimode LISWs.

Multi-level diffractive optical elements produced by excimer laser ablation of sol-gel.

Material ablation by excimer laser micromachining is a promising approach for structuring sol-gel materials as we demonstrate in the present study. Using the well-known direct etching technique, the behaviour of different hybrid organic/inorganic self-made sol-gel materials is examined with a KrF* laser. Ablated depths ranging from 0.1 to 1.5 microm are obtained with a few laser pulses at low fluence (< 1 J/cm(2)). The aim is to rapidly transfer surface relief multi-level diffractive patterns in such a substrate, without intermediate steps. The combination with the 3D profilometry technique of coherence probe microscopy permits to analyse the etching process with the aim of producing multi-level Diffractive Optical Elements (DOE). Examples of four-level DOEs with 10 microm square elementary cells are presented, as well as their laser reconstructions in the infrared.

Synthesis of chromophores combining second harmonic generation and two photon induced fluorescence properties.

The design of new chromophores presenting simultaneous SHG and TPEF properties is reported.

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.

Quasi-solitonic behavior of self-written waveguides created by photopolymerization.

We investigated the condition of unique self-written channel and multichannel propagation inside bulk photopolymerizable materials. Light was introduced in the medium by a single-mode optical fiber. At a very low beam power of 5 muW , a unique uniform-channel waveguide without any broadening was obtained by polymerization. When the input power is increased to 100 muW , the guide becomes chaotic and multichannel. We connected two fibers separated by a 1-cm distance. The results open the door to studies of the optical and electro-optical properties of photopolymerized guides doped by nonlinear optical chromophores and to possible applications in integrated optical devices.