A combined theoretical and experimental investigation on the influence of the bromine substitution pattern on the photophysics of conjugated organic chromophores.

A large series of structurally related two-photon photosensitizers with heavy atom substitution were synthesized and evaluated through a combined spectroscopic (steady-state and time resolved), photophysical and computational study. Our aim was to identify some relevant parameters related to their excited state dynamics including photo-induced singlet oxygen generation. Although these dynamics result from the interplay of many factors, we show that the triplet excited state generation kinetics can generally be correlated with the calculated values of both the spin-orbit coupling and the energy gap between S1 and T1 states, which themselves mostly depend on the positioning of the heavy atoms along the π-conjugated structure rather than their number.

Photophysical, amplified spontaneous emission and charge transport properties of oligofluorene derivatives in thin films.

We investigate the photophysical and amplified spontaneous emission properties of a series of monodisperse solution-processable oligofluorenes functionalized with hexyl chains at the C9 position of each fluorene unit. Thin films of these oligofluorenes are then used in organic field-effect transistors and their charge transport properties are examined. We have particularly focused our attention on the influence of oligofluorene length on the absorption and steady-state fluorescence spectra, on the HOMO/LUMO energy levels, on the photoluminescence lifetime and quantum yield as well as on the amplified spontaneous emission properties and the charge carrier mobilities. Differential scanning calorimetry and X-ray diffraction measurements demonstrate that, among all oligofluorene derivatives used in this study, only the structure and morphology of the pentafluorene film is significantly modified by a thermal treatment above the glass transition temperature, resulting in a 9 nm blue-shift of the fluorescence spectrum without significant changes in the photoluminescence quantum yield and in the amplified spontaneous emission threshold. In parallel, hole field-effect mobility is significantly increased from 8.6 × 10(-7) to 3.8 × 10(-5) cm(2) V(-1) s(-1) upon thermal treatment, due to an increase of crystallinity. This study provides useful insights into the morphological control of oligofluorene thin films and how it affects their photophysical and charge transport properties. Moreover, we provide evidence that, because of the low threshold, the tunability of the amplified spontaneous emission and the photostability of the films, these oligofluorenes are promising candidates for organic solid-state laser applications.

Polarization effect on the two-photon absorption of a chiral compound.

In this report, we investigate the polarization effect (linear, elliptical and circular) on the two-photon absorption (2PA) properties of a chiral compound based in azoaromatic moieties using the femtosecond Z-scan technique with low repetition rate and low pulse energy. We observed a strong 2PA modulation between 800 nm and 960 nm as a function the polarization changes from linear through elliptical to circular. Such results were interpreted employing the sum-over-essential states approach, which allowed us to model the 2PA circular-linear dichroism effect and to identifier the overlapping of the excited electronic states responsible by the 2PA allowed band.

Ancient Greek text concealed on the back of unrolled papyrus revealed through shortwave-infrared hyperspectral imaging.

Only a few Herculaneum rolls exhibit writing on their reverse side. Since unrolled papyri are permanently glued to paperboard, so far, this fact was known to us only from 18th-century drawings. The application of shortwave-infrared (SWIR; 1000-2500 nm) hyperspectral imaging (HSI) to one of them (PHerc. 1691/1021) has revealed portions of Greek text hidden on the back more than 220 years after their first discovery, making it possible to recover this primary source for the ongoing new edition of this precious book. SWIR HSI has produced better contrast and legibility even on the extensive text preserved on the front compared to former imaging of Herculaneum papyri at 950 nm (improperly called multispectral imaging), with a substantial impact on the text reconstruction. These promising results confirm the importance of advanced techniques applied to ancient carbonized papyri and open the way to a better investigation of hundreds of other such papyri.

A Fluorescent Polymer Probe with High Selectivity toward Vascular Endothelial Cells for and beyond Noninvasive Two-Photon Intravital Imaging of Brain Vasculature.

A chromophore-engineering strategy that relies on the introduction of a ground-state distortion in a quadrupolar chromophore was used to obtain a quasi-quadrupolar chromophore with red emission and large two-photon absorption (2PA) cross-section in polar solvents. This molecule was functionalized with water-solubilizing polymer chains. It constitutes not only a remarkable contrast agent for intravital two-photon microscopy of the functional cerebral vasculature in a minimally invasive configuration but presents intriguing endothelial staining ability that makes it a valuable probe for premortem histological staining.

Finite element modeling of the radiative properties of Morpho butterfly wing scales.

With the aim of furthering the explanation of iridescence in Morpho butterflies, we developed an optical model based on the finite-element (FE) method, taking more accurately into account the exact morphology of the wing, origin of iridescence. We modeled the photonic structure of a basal scale of the Morpho rhetenor wing as a three-dimensional object, infinite in one direction, with a shape copied from a TEM image, and made out of a slightly absorbing dielectric material. Periodic boundary conditions were used in the FE method to model the wing periodic structure and perfectly matched layers permitted the free-space scattering computation. Our results are twofold: first, we verified on a simpler structure, that our model yields the same result as the rigorous coupled wave analysis (RCWA), and second, we demonstrated that it is necessary to assume an absorption gradient in the true structure, to account for experimental reflectivity measured on a real wing.

Novel ruthenium(II) and zinc(II) complexes for two-photon absorption related applications.

Two new fluorene derivatized 1,10-phenanthroline ligands and related tris-chelate Ru(II) or Zn(II) coordination complexes have been synthesised. The linear and nonlinear (two-photon induced fluorescence) photophysical measurements have contributed to highlight the possibility to tune the absorption spectral range and excited lifetime, depending on ligand substitution and nature of the metal. More significantly, the observation of two-photon absorption (TPA) associated with long-lived metal-to-ligand charge-transfer (MLCT) excited states in the Ru(II)-based chromophores, opens a wide range of applications in the near infrared.