Quadrupolar benzobisthiazole-cored arylamines as highly efficient two-photon absorbing fluorophores.

A computer-aided design of novel D-π-A-π-D styrylamines containing five isomeric benzobisthiazole moieties as the electron-accepting core has revealed the linear centrosymmetric benzo[1,2-d:4,5-d']bisthiazole as the most promising building block for engineering chromophores displaying high two-photon absorption (TPA) in the near-IR region, as also confirmed experimentally. The ease of synthesis of quadrupolar derivatives thereof, combined with extraordinarly high TPA action cross sections (δTPAΦf > 1500 GM), makes these heteroaromatic systems particularly attractive as diagnostic agents in 3D fluorescence imaging.

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-pi-acceptor-pi-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- and three-photon absorption of organic ionic pyrylium based materials.

Pyrylium dyes having the same basic chemical structure, differing only to a specific substituent, have been used as novel materials for multiphoton three-dimensional data storage. Electronic absorption spectra, two-photon and three-photon absorption properties of this class of pyrylium dyes, have been studied theoretically and compared to experimental results. The effects of the counteranion, the surrounding solvent, and electron releasing and electron withdrawing groups in specific positions of the basic structure have been explored in detail. It is argued that on grounds of the quality of experimental spectroscopic agreement, the computed two- and three-photon data may be used in pulse propagation simulations of three-dimensional recording in optical memories.

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.

Influence of aggregates and solvent aromaticity on the emission of conjugated polymers.

The influence of aggregates and solvent aromaticity on the photophysics and fluorescence dynamics of two conjugated polymers is studied. The two polymers are derivatives of poly(p-phenylene vinylene) (PPV) containing different kinked moieties along the main chain. The polymers contain 2,6-diphenylpyridine and m-terphenyl kinked moieties and they are abbreviated as PN and PC, respectively. The insertion of kinked segments along the main chain shifts the emission spectrum from the yellow-orange spectral region, common to PPV derivatives, to the blue-green spectral region. The results show that in dilute solutions the polymers decay monoexponentially, while in concentrated ones the fluorescence decays biexponentially, indicating fluorescence quenching. This is attributed to an energy transfer process from polymer chains to aggregates that occurs within a few tens of picoseconds. By comparing the photophysics and fluorescence dynamics of polymer PN in a nonaromatic and an aromatic solvent, we conclude that the polymer conformation adopted in the aromatic solvent leads to a higher fluorescence quantum yield and a longer fluorescence lifetime. Furthermore, the fluorescence quenching of PN because of aggregates is faster and more efficient in the aromatic than in the nonaromatic solvent. These results can be explained through a more extended chain conformation of PN in the aromatic solvent.

Femtosecond time resolved fluorescence dynamics of a cationic water-soluble poly(fluorenevinylene-co-phenylenevinylene).

A recently synthesized cationic water-soluble poly(fluorenevinylene-co-phenylenevinylene) was studied by means of steady state and femtosecond time resolved upconversion spectroscopy in aqueous and EtOH solutions. Steady state spectroscopic measurements showed that the polymer emits at the blue-green spectral region and that aggregates are formed in concentrated polymer solutions. The fluorescence dynamics of the polymer in concentrated solutions, studied at a range of emission wavelengths, exhibited a wavelength dependent and multiexponential decay, indicating the existence of various decay mechanisms. Specifically, a rapid decay at short emission wavelengths and a slow rise at long wavelengths were observed. Both features reveal an energy transfer process from isolated to aggregated chains. The contribution of the energy transfer process as well as of the isolated chains and the aggregates on the overall fluorescence decay of the polymer was determined. The dependence of the energy transfer rate and efficiency on polymer concentration was also examined.

Substituent effect on the photobleaching of pyrylium salts under ultrashort pulsed illumination.

The current article presents the photobleaching properties of a group of pyrylium salts under ultrashort pulsed illumination. These pyrylium salts have the same basic chemical structure and differ only by a specific substituent. It is proven experimentally that two different mechanisms are simultaneously present to the photobleaching of all molecules studied (independently of their specific chemical structure). However, the particular parameters of each mechanism are influenced significantly by the substituent change. The experimental investigation of these parameters showed the presence of multiphoton interactions in the photobleaching of pyrylium salts depending essentially on the specific substituent.

Study of the isotropic and anisotropic fluorescence of two oligothiophenes by femtosecond time-resolved spectroscopy.

The excited-state dynamics of two oligothiophenes, 5,5'-dicarboxyhaldehyde 2,2',5',2' '-terthiophene and 5-carboxyhaldehyde 2,2',5',2' '-terthiophene, were studied by time-resolved fluorescence spectroscopy, in the femtosecond regime. The isotropic and anisotropic parameters of their fluorescence were calculated. The angle (alpha) between the absorption and emission molecular dipoles was estimated from the initial fluorescence anisotropy. The effect of the chemical substituents, at the ends of the main chain of the molecule, on the temporal behavior of the fluorescence was investigated. Particularly, the nonsymmetric oligothiophene molecule (containing one aldehyde group) exhibits shorter excited-state isotropic decay time than the symmetric one (containing two aldehyde groups). This is due to the higher value of the emission dipole moment of the nonsymmetric oligothiophene in comparison with that of the symmetric one. Additionally, the two materials have almost the same anisotropic fluorescence parameters, and this is attributed to the same rotational motions in the excited state due to their similar molecular structures.