P. Persephonis

Benzothiazoles with Tunable Electron-Withdrawing Strength and Reverse Polarity: A Route to Triphenylamine-Based Chromophores with Enhanced Two-Photon Absorption

A series of dipolar and octupolar triphenylamine-derived dyes containing a benzothiazole positioned in the matched or mismatched fashion have been designed and synthesized via palladium-catalyzed Sonogashira cross-coupling reactions. Linear and nonlinear optical properties of the designed molecules were tuned by an additional electron-withdrawing group (EWG) and by changing the relative positions of the donor and acceptor substituents on the heterocyclic ring. This allowed us to examine the effect of positional isomerism and extend the structure-property relationships useful in the engineering of novel heteroaromatic-based systems with enhanced two-photon absorption (TPA). The TPA cross-sections (δ(TPA)) in the target compounds dramatically increased with the branching of the triphenylamine core and with the strength of the auxiliary acceptor. In addition, a change from the commonly used polarity in push-pull benzothiazoles to a reverse one has been revealed as a particularly useful strategy (regioisomeric control) for enhancing TPA cross-sections and shifting the absorption and emission maxima to longer wavelengths. The maximum TPA cross-sections of the star-shaped three-branched triphenylamines are ∼500-2300 GM in the near-infrared region (740-810 nm); thereby the molecular weight normalized δ(TPA)/MW values of the best performing dyes within the series (2.0-2.4 GM·g(-1)·mol) are comparable to those of the most efficient TPA chromophores reported to date. The large TPA cross-sections combined with high emission quantum yields and large Stokes shifts make these compounds excellent candidates for various TPA applications, including two-photon fluorescence microscopy.

Benzothiazole-Based Fluorophores of Donor−π-Acceptor−π-Donor Type Displaying High Two-Photon Absorption

A series of novel heterocycle-based dyes with donor-pi-bridge-acceptor-pi-bridge-donor (D-pi-A-pi-D) structural motif, where benzothiazole serves as an electron-withdrawing core, have been designed and synthesized via palladium-catalyzed Sonogashira and Suzuki-type cross-coupling reactions. All the target chromophores show strong one-photon and two-photon excited emission. The maximum two-photon absorption (TPA) cross sections delta(TPA) of the prepared derivatives bearing diphenylamino functionalities occur at wavelengths ranging from 760 to 800 nm and are as large as approximately 900-1100 GM. One- and two-photon absorption characteristics of the title dyes have also been investigated by using density functional theory (DFT) and the structure-property relationships are discussed. The TPA cross sections calculated by means of quadratic response time-dependent DFT using the Coulomb-attenuated CAM-B3LYP functional support the experimentally observed trends within the series, as well as higher delta(TPA) values of the title compounds compared to those of analogous fluorene or carbazole-derived dyes. In contrast, the traditional B3LYP functional was not successful in predicting the observed trend of TPA cross sections for systems with different central cores. In general, structural modification of the pi-bridge composition by replacement of ethynylene (alkyne) with E-ethenylene (alkene) linkages and/or replacement of dialkylamino electron-donating edge substituents by diarylamino ones results in an increase of delta(TPA) values. The combination of large TPA cross sections and high emission quantum yields makes the title benzothiazole-based dyes attractive for applications involving two-photon excited fluorescence (TPEF).

Two-photon absorption properties of novel organic materials for three-dimensional optical memories

Abstract The two-photon absorption (TPA) properties of a novel group of pyrylium-based compounds were studied. The molecules of this group were synthesized by systematically changing the chemical structure of a specific substituent in an initial chromophore. TPA cross-sections as large as 1.8×10 −47 cm 4 s photon −1 and high quantum yields were obtained. The results combined with the low cost and ease of synthesis of these compounds make them candidates for TPA applications. Particularly, three-dimensional data storage in polymer matrices of the synthesized compounds was realized through the photobleaching process. The high efficiency of recording and the submicron resolution reveal the great potential of this group of molecules as memory materials.

Intensity dependent nonlinear absorption of pyrylium chromophores

Abstract The intensity dependence of nonlinear absorption (NLA) of a series of pyrylium chromophores was studied with femtosecond pulses in their two-photon absorption spectral region to assess their potential as optical limiters. The open z-scan technique using different excitation intensities was employed. Fifth-order effects appear above a critical value of the irradiance and consequently of the first excited singlet-state population. Reverse saturable absorption (RSA) based on two-photon (TPA) and excited-state absorption (ESA) was dominant in most cases. The third- and fifth-order NLA coefficients and high ESA cross-sections of the order of 10 −15 cm 2 are presented at 760, 790 and 840 nm.

The inductance of the discharge in a spark gap

The inductance of an arc discharge has been modeled and a mathematical formula given for the arc inductance in terms of its geometrical dimensions. This formula agrees with the experimental results and is used to determine the arc‐channel radius. Inductance measurements have been taken for various values of pressure, interelectrode distance and applied voltage in a triggered spark gap. The dependence of inductance upon these parameters has been explained through the existing variations of the arc‐channel cross section. Two mechanisms are responsible for the variations of inductance. The first is diffusion and the second is the tendency of the current channel to vary diameter with pressure, interelectrode distance, and applied voltage. The time history of the arc‐channel inductance has been investigated. Finally, the ambipolar diffusion coefficient and the total charge number of the arc channel has been obtained.

Novel class of pyrylium dyes with high efficiency in lasing and two-photon absorption fluorescence

Abstract We report the synthesis of a promising class of pyrylium dyes concerning laser and two-photon absorption action. Three representatives of this class, 4-(2,4-dichlorophenyl)-2,6-bisphenylpyrylium tetrafluoroborate, 4-phenyl-2,6-bis(4-methoxyphenyl)pyrylium tetrafluoroborate, and 4-(2,4-dichlorophenyl)-2,6-bis(4-biphenyl)pyrylium tetrafluoroborate, were investigated. Each dye was synthesized by a convenient and inexpensive method. Efficient laser action was shown at ∼500, ∼560, ∼615 nm. Changing the conjugation length i.e. the length of the oligophenyl moiety, or introducing various substituents on the aromatic rings, the emission maximum can be controlled. Two-photon absorption induced fluorescence was also observed. These pyrylium dyes constitute excellent candidates for laser technology and two-photon absorption applications.

Three-photon induced photobleaching in a three-dimensional memory material

The photobleaching properties of a 3D memory material based on pyrylium salts are studied. It is shown that under ultrashort pulsed irradiation photobleaching occurs through two diverse mechanisms. One is major and causes fast bleaching, whereas the other is minor and causes slow bleaching. Furthermore, it is proved that both mechanisms are three- or more-photon processes. This fact gives the capability of significantly increasing data storage density.

Z-scan analysis for near-Gaussian beams through Hermite-Gaussian decomposition

Gaussian decomposition is used as a theoretical infrastructure with which Z-scan experiments are analyzed. This procedure is extended here to the interesting, from a practical point of view, case in which the laser beam used is not perfectly Gaussian. We follow a perturbative approach to obtain the far-field pattern of the beam after the beam passes through a nonlinear sample. The procedure is based on the decomposition of the electric field at the exit plane of the sample to a linear combination of Hermite–Gaussian functions. To a first-order approximation, each mode of the incident beam is decomposed to a linear combination of different-order modes that do not exceed the order of the original mode. Finally, the effects of the simultaneous presence of first and higher-order refractive nonlinearities or first-order refractive nonlinearity and nonlinear absorption are studied.

Strong two photon absorption and photophysical properties of symmetrical chromophores with electron accepting edge substituents.

Two photon absorption (TPA) and photophysical properties of three new symmetrical chromophores with electron accepting phthalimide edge substituents have been studied. The three chromophores contain fluorene, alcoxy-substituted divinyl benzene, and carbazole moieties as central cores, respectively. The femtosecond time-resolved fluorescence upconversion spectroscopy and two photon excited fluorescence technique have been carried out. The effect of solvent polarity on TPA and on photophysics has also been determined. Ultrafast fluorescence dynamics, with decay times ranging from 1 to 13 ps, are revealed in polar solvents. This is attributed to the relaxation of the chromophores to the intramolecular charge transfer state. The chromophore bearing fluorene central core, being of the type A-pi-A, is the most efficient concerning TPA. Strong TPA, with a cross section value as high as 2100 GM at an excitation wavelength of 770 nm is found in acetophenone which is a solvent of intermediate polarity. The TPA spectra were also reproduced using a sum over states three-state model. A study of the TPA induced photobleaching of the fluorene molecule, doped in a solid poly(methyl-methacrylate) film, has shown that this material is very promising for efficient TPA optical data storage.

The influence of the external circuit on arc-discharge of a spark-gap: its application to a pulsed gas laser

An investigation of the influence of the driving circuit on the arc-discharge of a spark-gap takes place in this work. The two most common types of circuits used in pulsed gas lasers have been studied for all possible combinations of capacitance allocation. In these circuits the spark-gap is used as ignition system and participates in the electric circuit through its resistance and inductance. This consideration shows that capacitances act as charge containers and feed the arc-discharge in the spark-gap independently of their positions in the circuit. Their values influence the total charge contained in the arc discharge and this, in its turn, influences the discharge resistance. On the other hand, total charge flows through the discharge at a rate determined by the coupling of the circuit loops, namely, by the circuit type. Thus, circuit type influences the drift velocity and this, in its turn, influences the channel radius, which determines the discharge inductance. >