Resonant nonlinear absorption in Zn-phthalocyanines

In this work, we investigate the nonlinear absorption dynamics of Zn phthalocyanine in dimethyl sulfoxide (DMSO). We used single pulse and pulse train Z-scan techniques to determine the dynamics and absorption cross-sections of singlet and triplet states at 532 nm. The excited singlet state absorption cross-section was determined to be 3.2 times higher than the ground state one, giving rise to reverse saturable absorption. We also observed that reverse saturable absorption occurs from the triplet state, after its population by intersystem crossing, whose characteristic time was determined to be 8.9 ns. The triplet state absorption cross-section determined is 2.6 times higher than the ground state one. In addition, we used the white light continuum Z-scan to evaluate the singlet excited state spectrum from 450 to 710 nm. The results show two well-defined regions, one above 600 nm, where reverse saturable absorption is predominant. Below 600 nm, we detected a strong saturable absorption. A three-energy-level diagram was used to explain the experimental results, leading to the excited state absorption cross-section determination from 450 nm up to 710 nm.FAPESPCNPQAFOSR (FA9550- 07-1-0374

Birefringent microstructures fabricated by two-photon polymerization containing an azopolymer

Birefringent materials have many applications in optical devices. An approach to obtain optically induced birefringence is to employ a guesthost strategy, using a polymer matrix containing an azodye. However, such method normally leads to low residual birefringence. Therefore, methodologies to produce microstructures with optimized birefringence are still on demand. Here we report on the fabrication, using two-photon polymerization, and characterization of birefringent microstructures produced in a polymer blend containing an azopolymer. Such microstructures present good structural integrity and residual birefringence of approximately 35 percent, depending on the sample formulation used, which indicates this approach for the fabrication of microoptical devices.FAPESPCNPqCAPE

Understanding the two-photon absorption spectrum of PE2 platinum acetylide complex

Herein, we report on the two-absorption cross-section spectrum of trans-Pt(PBu3)2 (C≡C-C6H4-C≡C-C6H5)2 (PE2) platinum acetylide complex employing the femtosecond wavelength-tunable Z-scan technique. The PE2 complex can be visualized as two branches containing two phenylacetylene units, each one linked by a platinum center, completely transparent in the visible region. Because of this structure, large delocalization of π-electrons allied to the strong intramolecular interaction between the branches is expected. The 2PA absorption spectrum was measured using the femtosecond wavelength-tunable Z-scan technique with low repetition rate (1 kHz), in order to obtain the 2PA spectrum without excited-state contributions. Our results reveal that PE2 in dichloromethane solution presents two 2PA allowed bands located at 570 and 710 nm, with cross section of about 320 and 45 GM, respectively. The first one is related to the strong intramolecular interaction between the molecule’s branches due to the presence of platinum atom, while the second one is associated with the breaking of symmetry of the chromophore in solution due, most probably to a large twisting angle of the ligand’s phenyl rings relative to the Pt core.FAPESP (11/06489-6; 11/12399-0)CNPqCAPESAFOSR (FA9550-12-1-0028

Dye aggregation and influence of pre-micelles on heterogeneous catalysis: a photophysical approach

Common cationic dyes used for laser and fluorescent probes present low solubility in water. In order to increase the dye concentration in aqueous solutions, anionic surfactant can be added. The strong interaction between anionic surfactant and cationic dye can affect drastically the dye absorption and fluorescence properties. Here we observed that the fluorescence of the species in aqueous solution is maximized at condition of complete micellization of surfactants at critical micelle concentration (CMC). In addition, combined measurements of absorption, emission and fluorescence lifetime provide fundamental information on the critical concentration of H-aggregates formation and monomer separation, induced by pre-micelles and homomicelles on different surfactant sodium dodecylsulphate (SDS) concentration. The experimental results show how to find precisely the critical concentration of H-aggregates by optical method in two different xanthene-derived molecules: rhodamine 6G and rhodamine B. The adequate transference of electron from excited dye to the conduction band of semiconductor (TiO2) promotes the creation of reactive species that provides the degradation of dye with advantage of use of irradiation in the visible region and strong photobleaching with direct exposure to the visible light irradiation in a scale of time of 10 min

Synthesis and two-photon absorption property of novel salen complexes incorporated with two pendant azo dyes

New salen compounds have been developed to possess two pendant azo dye chromophores. The two-photon absorption properties have been observed which result from the chromophores. The additive property has been found to exist as a result of no detrimental dipole–dipole interaction between chromophores.NASA (NCC3-552)NSF (# HRD-0630456)FAPES

Synthesis and characterization of copolymers of alkyl- and azo-thiophenes: chromic properties and photoinduced birefringence

Polyazothiophene is a type of polythiophene derivative that combines the electrical and luminescent properties of polythiophenes with the photoisomerization property of azopolymers. Extensive efforts have been made to improve the properties of polyazothiophenes, such as solubility, optical, and chromic properties. We report the preparation of copolymers of an alkylthiophene (3-octylthiophene, 3-OT) and an azothiophene (2-[N-ethyl-N-[4-[(4-(4-nitrophenyl)azo]phenyl]amino]ethyl 3-thienylacetate, 3-AzoT) in different ratios as an alternative route to improve these properties. The azosubstituted monomer contents in these copolymers were 6, 9, 12, and 51% (in mol), as evaluated by elemental analysis. Their chemical structures were confirmed by FTIR and 1H-NMR. HPSEC and thermal analysis were used to characterize the polymers. The presence of thermochromic and solvatochromic properties was demonstrated by UV-Vis spectroscopy. Optically induced birefringence was detected only in polymers with 12 and 51 mol % of azo-units. The introduction of different ratios of the azothiophene in the copolymer alters the polymer solubility and emissive properties. The results indicate that the polyazothiophene copolymers presented are promising active layers for optical devices and sensor

Broadband three-photon absorption spectra of platinum acetylide complexes

We investigate the three-photon absorption spectra of four platinum acetylides complexes employing femtosecond pulses. We observed strong three-photon absorption cross-section in the near-infrared region (from 850 nm to 1200 nm). The three-photon absorption (3PA) spectra present resonance enhancement effect as two photons of the excitation wavelength approach the lower two-photon allowed states of the molecules as well as a 3PA allowed band around 1180 nm. The 3PA cross-section spectra were interpreted using the sum-over-essential-states approach, considering a three-energy-level diagram.FAPESPCNPqCAPESAFOSR (FA9550-07-1-0374

Broadband three-photon absorption spectra of platinum acetylide complexes

We investigate the three-photon absorption spectra of four platinum acetylides complexes employing femtosecond pulses. We observed strong three-photon absorption cross-section in the near-infrared region (from 850 nm to 1200 nm). The three-photon absorption (3PA) spectra present resonance enhancement effect as two photons of the excitation wavelength approach the lower two-photon allowed states of the molecules as well as a 3PA allowed band around 1180 nm. The 3PA cross-section spectra were interpreted using the sum-over-essential-states approach, considering a three-energy-level diagram.FAPESPCNPqCAPESAFOSR (FA9550-07-1-0374

Ultrafast dynamics of bis (n-butylimido) perylene thin films excited by two-photon absorption

We report a pump-probe study of the two-photon induced reflectivity changes in bis (n-butylimido) perylene thin films. To enhance the two-photon excitation we deposited bis (n-butylimido) perylene films on top of gold nanoislands. The observed transient response in the reflectivity spectrum of bis (n-butylimido) perylene is due to a depletion of the molecule’s ground state and excited state absorption.National Science Foundation (DMI-0334984)Army Research Office (W911NF-05-1-0471)FAPESPCAPES

Femtosecond Two-Photon Absorption Spectroscopy Of Copper Indium Sulfide Quantum Dots: A Structure-Optical Properties Relationship

We have interpreted the two-photon absorption spectrum of water-soluble copper indium sulfide (CIS) QDs with stoichiometry 0.18 (Cu), 0.42 (In), and 2 (S) and an average diameter of approximately 2.6 nm. For that, we employed the wavelength-tunable femtosecond Z-scan technique and the parabolic effective-mass approximation model, in which the excitonic transition energies were phenomenologically corrected due to the stoichiometry of the nanocrystal. This model considers a conduction band and three valence sub-bands allowing excitonic transitions via centrosymmetric (Δl = ±1, where l is the angular momentum of the absorbing state) and non-centrosymmetric (Δl = 0) channels. In such case, this became relevant because the CIS QDs with chalcopyrite crystalline structure is a non-centrosymmetric semiconductor. Thus, our experimental results pointed out two 2 PA allowed bands located at 715 nm (2hv = 3.47 eV) and 625 nm (2hv = 3.97 eV) with cross sections of (6.3 ± 1.0) x 102 GM and (4.5 ± 0.7) x 102 GM, respectively. According to the theoretical model, these 2 PA bands can be ascribed to the 1P1/2(h3) → 1S3/2(e) (lower energy band) and 1P1/2(hheavy) → 1S3/2(e) (90%)/(10%)1P1/2(hsplit-off) → 1P3/2(e) (higher energy band) excitonic transitions. A good agreement (magnitude and spectral position) between the experimental and theoretical data were obtained. However, our experimental data suggest that the higher-energy 2 PA band may have other contributions due to the mixing between the heavy- and the light-hole bands, which the effective mass model does not take into consideration