Red-edge-wavelength finely-tunable laser action from new BODIPY dyes.

New BODIPY dyes with two 4-formylphenyl, 4-(2,2-dimethoxycarbonylvinyl)phenyl and 4-(2,2-dicyanovinyl)phenyl groups at the 3- and 5-positions have been successfully designed and synthesized via palladium-catalyzed coupling reaction or Knoevenagel-type condensations. Structural modification of the BODIPY core via conjugation-extending residues significantly affects the spectroscopy and photophysical properties of the BODIPY fluorophore. These substituents cause the largest bathochromic shift in both absorption and emission spectra, which are shifted toward the red compared to its 4-phenylsubstituted analogue. Additionally, the fluorescence quantum yields and the Stokes shifts are also significantly higher than the corresponding phenyl-substituted dye. New BODIPY dyes have a high laser photostability, superior to that of commercial dyes with laser emission in the same spectral region, such as Perylene Red and Rhodamine 640. The substitution introduced in these derivatives allows to obtain tunable laser emission with a bandwidth of 0.15 cm(-1) and a tuning range of up to 50 nm. So with these three dyes it is possible to cover the spectral range 590-680 nm in a continuous way and with stable laser emission and small linewidth.

Photophysical and laser emission studies of 8-polyphenylene-substituted BODIPY dyes in liquid solution and in solid polymeric matrices.

In our search for efficient and photostable laser dyes, four new dyes with the basic structure of the commercial BODIPY laser dye PM567, with either an 8-diphenylene or an 8-p-triphenylene group, both substituted at the terminal polyphenylene position with an acetoxymethyl (dyes P2Ar1Ac and P3Ar1Ac, respectively) or a methacryloyloxymethyl group (dyes P2Ar1MA and P3Ar1MA, respectively), have been synthesized. The photophysical and lasing properties of the dyes have been studied both dissolved in liquid solvents (acetoxymethyl dyes) and incorporated into solid polymeric matrices, in the latter case as solutions (acetoxymethyl dyes) or as copolymers with methyl methacrylate (methacryloyloxymethyl dyes). In liquid solution, the photophysics of P2Ar1Ac and P3Ar1Ac is scarcely affected by the number (two or three) of p-phenylene units. Quantum mechanical calculations reveal that the p-phenylene units in these dyes are twisted ca. 37 degrees each other, an that the first 8-p-phenylene group stands nearly perpendicular to the aromatic BODIPY plane, resulting in electronic decoupling of the two chromophores. P2Ar1Ac exhibits a somewhat lower photodegradation quantum yield under UV and visible irradiation, if compared with P3Ar1Ac or with PM567, likely because of its also lower rate constant for the reaction with in situ-generated singlet molecular oxygen. Both acetoxymethyl dyes emit laser radiation in solution in all the solvents tried, under transversal pumping at 532 nm. In ethyl acetate, with a dye concentration of 0.80 x 10(-3) M, laser efficiencies as high as 80% have been observed. When the 8-polyphenylene dyes were incorporated into solid poly(methyl methacrylate) (PMMA) matrices, as solutions or as copolymers, the fluorescence emission increased with respect to that of the parent PM567 dye dissolved in the same matrix, and lasing efficiencies in the range 18-31% were obtained, with good photostability. The dye P2Ar1Ac dissolved in PMMA was found to exhibit the best overall laser behavior, with a good balance between efficiency and photostability.

Characterization of rhodamine 6G aggregates intercalated in solid thin films of laponite clay. 2 Fluorescence spectroscopy.

The photoluminescence response of Rhodamine 6G (R6G) laser dye intercalated into solid thin films of Laponite (Lap) clay is studied as a function of dye loading. Fluorescence spectroscopy (steady-state and time-resolved techniques) was used to characterize the R6G species adsorbed into the solid films. For very diluted R6G loadings (40% CEC), with a reminiscent fluorescence band at around 600 nm.

Intramolecular charge transfer in pyrromethene laser dyes: photophysical behaviour of PM650.

Absorption and fluorescence (steady-state and time-correlated) techniques are used to study the photophysical characteristics of the pyrromethene 650 (PM650) dye. The presence of the cyano group at the 8 position considerably shifts the absorption and fluorescence bands to lower energies with respect to other related pyrromethene dyes; this is attributed to the strong electron-acceptor character of the cyano group, as is theoretically confirmed by quantum mechanical methods. The fluorescence properties of PM650 are intensively solvent-dependent. The fluorescence band is shifted to lower energies in polar/protic solutions, and the evolution of the corresponding wavelength with the solvent is analysed by a multicomponent linear regression. The fluorescence quantum yield and the lifetime strongly decrease in polar/protic solvents, which can be ascribed to an extra nonradiative deactivation, via an intramolecular charge-transfer state (ICT state), favoured in polar media.

Characterization of supported solid thin films of Laponite clay. Intercalation of rhodamine 6G laser dye.

The morphology of thin films of Laponite (Lap) clay elaborated by the evaporation method and spin-coating technique was analyzed by atomic force microscopy and scanning electron microscopy, indicating a better quality film for the latter procedure. Rhodamine 6G (R6G) laser dye was intercalated into these films by ion exchange mechanism, performed by immersing the clay film into adequate dye solutions in which the effect of the dye concentration, immersion time, and nature of the solvent on the adsorption process were checked. The adsorption of R6G at the interlayer space of Lap was analyzed by the X-ray diffraction technique, and the presence of several R6G species (monomers and aggregates) was characterized by absorption and fluorescence spectroscopies. Less viscous solvents lead to higher dye loadings, suggesting a diffusional process for the intercalation of the dye in the interlayer spaces of Lap, and polar solvents favor the swellability of the interlayer space giving rise to a more homogeneous distribution of R6G molecules through the film and decreasing the dye aggregation. With the aging of the samples, the dye molecules can migrate through the interlayer spaces, leading to a more expanded distribution of R6G molecules and to the dye deaggregation.

Photophysical and lasing properties of new analogs of the boron-dipyrromethene laser dye pyrromethene 567 incorporated into or covalently bounded to solid matrices of poly(methyl methacrylate).

The photophysical, lasing and thermostability properties of newly synthesized analogs of the commercial dye pyrromethene 567 (PM567) have been measured in polymeric matrices of poly(methyl methacrylate) both when used as a dopant and when covalently bounded to the polymeric chain. These analogs have an acetoxy or a polymerizable methacryloyloxy group at the end of a polymethylene chain at Position 8 of the PM567 chromophore core. Clear correlations between photophysical and lasing characteristics are observed. Linking chain lengths with three or more methylene units give the highest fluorescence quantum yields (as high as 0.89) and lasing efficiencies (as high as 41%). The covalent linkage of the chromophore to the polymeric chain via the methacryloyloxy group improves the photostability of the PM567 chromophore.