Teresa Arbeloa

Structural, photophysical and lasing properties of pyrromethene dyes

The molecular structure and the photophysical properties of pyrromethene-BF2 (PM) dyes are studied with the aim of finding the best structural and environmental conditions which optimize the laser performance of these dyes. To this end, UV–Vis absorption and fluorescence spectra and fluorescence decay curves of several PM dyes are registered in a multitude of solvents with different physicochemical properties and in polymeric solid matrices. Quantum mechanical calculations at different levels are also applied in order to explain the photophysical behaviour of these dyes. The studied pyrromethenes incorporate alkyl (methyl, ethyl and tert-butyl), sulfonate, cyano, and acetoxy- and methacryloyloxy-polymethylene groups in different positions of the chromophore. In the last case, the presence of the polymerizable acryloyl group facilitates the covalent linkage of the chromophore to a polymeric chain, of special technological interest in the development of tunable dye lasers in the solid state. From the experimental results and the theoretical calculations, we discuss different mechanisms of internal conversion for PM dyes, such as the loss in the planarity of the chromophore, the electron flow through the delocalized π-system, the vibrational coupling and the formation of an intramolecular charge transfer state. The present work demonstrates the good correlation between the photophysical and the lasing properties of PM dyes with different structural (substituents) and environmental (solvents and polymers) conditions. Contents PAGE 1. Introduction 340 2. Methodology 342 2.1. Dyes 342 2.2. Instrumental 344 2.3. Computational 345 3. Results and discussion 346 3.1. Preliminary considerations. Molecular structure 346 3.2. General photophysics 348 3.3. 2,6-Disubstituted-pyrromethenes 351 3.3.1. Solvent e.ect 355 3.3.2. Photophysics-lasing correlations 357 3.3.3. PM567 in polymeric matrices: cross-linking e.ect 357 3.4. Acetoxy-pyrromethenes 360 3.4.1. Linear 8-acetoxy analogues 361 3.4.2. 8-phenyl analogues 363 3.4.3. Solid polymeric matrices 365 3.5. 8-Cyano group: intramolecular charge transfer (ICT) state 367 4. Conclusions 371 Acknowledgements 371 References 372

New 8‐Amino‐BODIPY Derivatives: Surpassing Laser Dyes at Blue‐Edge Wavelengths

The development of highly efficient and stable blue-emitting dyes to overcome some of the most important shortcomings of available chromophores is of great technological importance for modern optical, analytical, electronic, and biological applications. Here, we report the design, synthesis and characterization of new tailor-made BODIPY dyes with efficient absorption and emission in the blue spectral region. The major challenge is the effective management of the electron-donor strength of the substitution pattern, in order to modulate the emission of these novel dyes over a wide spectral range (430-500 nm). A direct relationship between the electron-donor character of the substituent and the extension of the spectral hypsochromic shift is seen through the energy increase of the LUMO state. However, when the electron-donor character of the substituent is high enough, an intramolecular charge-transfer process appears to decrease the fluorescence ability of these dyes, especially in polar media. Some of the reported novel BODIPY dyes provide very high fluorescence quantum yields, close to unity, and large Stokes shifts, leading to highly efficient tunable dye lasers in the blue part of the spectrum; this so far remains an unexploited region with BODIPYs. In fact, under demanding transversal pumping conditions, the new dyes lase with unexpectedly high lasing efficiencies of up to 63 %, and also show high photostabilities, outperforming the laser action of other dyes considered as benchmarks in the same spectral region. Considering the easy synthetic protocol and the wide variety of possible substituents, we are confident that this strategy could be successfully extended for the development of efficient blue-edge emitting materials and devices, impelling biophotonic and optoelectronic applications.

On the arrangements of R6G molecules in organophilic C12TMA/lap clay films for low dye loadings.

Absorption and fluorescence spectroscopies with linearly polarized light are applied to characterize the adsorbed species of rhodamine 6G (R6G) laser dye in ordered organophilic laponite (Lap) clay films for low dye loadings. The organophilic character of the clay was controlled by the number of organic surfactant dodecyl-trimethylammonium (C12TMA) cations intercalated into the interlayer space of the clay. Experimental results suggest that for moderate to high surfactant contents (>70% of the total cation exchange capacity, CEC, of the clay) the accessibility of the interlayer space for R6G molecules is reduced. In these cases, the first stage in the adsorption of R6G molecules is at the external surface, where dye molecules can self-associate even for very low dye loading (around 0.1%CEC), probably for the limitation of the external surface area. The presence of a nonfluorescent H-type aggregate with a short-displaced coplanar structure and a fluorescent oblique head-to-tail J aggregate is reported. The inclined structure of this J aggregate is stabilized by the surfactant molecules at the external surface.

Scope and Limitations of the Liebeskind–Srogl Cross-Coupling Reactions Involving the Biellmann BODIPY

Several new examples of meso-(het)arylBODIPY were prepared via the Liebeskind-Srogl (L-S) cross-coupling reaction of the Biellmann BODIPYs (1a,b) and aryl- and heteroarylboronic acids in good to excellent yield. It was shown that this reaction could be carried out under microwave heating to shorten reaction times and/or increase the yield. It was illustrated that organostannanes also participate in the L-S reaction to give the corresponding BODIPY analogues in short reaction times and also with good to excellent yields. We analyze the role of the substituent at the sensitive meso position in the photophysical signatures of these compounds. In particular, the rotational motion of the aryl ring and the electron donor ability of the anchored moieties rule the nonradiative pathways and, hence, have a deep impact in the fluorescence efficiency.

Straightforward synthetic protocol for the introduction of stabilized c nucleophiles in the BODIPY core for advanced sensing and photonic applications

A straightforward synthetic protocol to directly incorporate stabilized 1,3-dicarbonyl C nucleophiles to the meso position of BODIPY (4,4-difluoro-4-bora-3a,4a-diaza-s-indacene) is reported. Soft nucleophiles generated by deprotonation of 1,3-dicarbonyl derivatives smoothly displace the 8-methylthio group from 8-(methylthio)BODIPY analogues in the presence of Cu(I) thiophenecarboxylate in stoichiometric amounts at room temperature. Seven highly fluorescent new derivatives are prepared with varying yields (20-92%) in short reaction times (5-30 min). The excellent photophysical properties of the new dyes allow focusing on applications never analyzed before for BODIPYs substituted with stabilized C nucleophiles such as pH sensors and lasers in liquid and solid state, highlighting the relevance of the synthetic protocol described in the present work. The attainment of these dyes, with strong UV absorption and highly efficient and stable laser emission in the green spectral region, concerns to one of the greatest challenges in the ongoing development of advanced photonic materials with relevant applications. In fact, organic dyes with emission in the green are the only ones that allow, by frequency-doubling processes, the generation of tunable ultraviolet (250-350 nm) radiation, with ultra-short pulses.

Adsorption of fluorescent R6G dye into organophilic C12TMA laponite films.

The absorption and fluorescence properties of rhodamine 6G (R6G) in organophilic laponite (Lap) clay films are studied. For this purpose, organo-Lap clays are synthesized by the incorporation of dodecyltrimethylammonium (C12TMA) as surfactant into the interlayer space of Lap clays. Two organo-Lap clays are prepared: one with moderate surfactant content (around 70% of the total cation-exchange capacity (CEC) of the clay) and a second with a high surfactant loading (about 130% CEC). Supported films are elaborated by the spin-coating technique and characterized by several techniques such as atomic force microscopy, elemental CHN analysis, X-ray diffraction, and thermogravimetry. IR spectroscopy reveals that the intercalation of R6G into organo-Lap films takes place at the detriment of the adsorbed C12TMA molecules. The photophysical properties of R6G monomers in the interlayer space of Lap films are improved by the presence of surfactant molecules. Moreover, organophilic environments can reduce the dye aggregation and favor the formation of fluorescent J-type aggregates, enhancing the fluorescence ability of dye/clay films with high dye contents. This improvement depends on the surfactant content.

FormylBODIPYs: Privileged Building Blocks for Multicomponent Reactions. The Case of the Passerini Reaction

Eleven formyl-containing BODIPY dyes were prepared by means of either the Liebeskind-Srogl cross-coupling reaction or the Vilsmeier reaction. These dyes were used as components in the Passerini reaction to give highly substituted BODIPY dyes. A joined spectroscopic and theoretical characterization of the synthesized compounds was conducted to unravel the impact of the structural rigidity/flexibility on the photophysical signatures. These dyes were tested as fluorescent trackers for phagocytosis. Additionally, they proved to be useful to stain different blood cells with an intense and stable signal at a very low exposure time.

Fluorescence Anisotropy to Study the Preferential Orientation of Fluorophores in Ordered Bi-Dimensional Systems: Rhodamine 6G/Laponite Layered Films

Absorption and fluorescence spectroscopies with linearly polarized light are applied to study the anisotropic behavior of a fluorescence dye (rhodamine 6G, R6G) adsorbed in ordered clay (laponite, Lap) particles. Films elaborated by the spin-coating technique provide a parallel stacking of clay layers in the supported substrates. The posterior intercalation of the R6G molecules into the interlayer space of Lap films with a preferential orientation with respect to the normal to the clay layers gives rise to a macroscopic orientation of dye molecules into the 2D surfaces. Such an organization induces an anisotropic behavior with a photoresponse of dye/clay films to the plane of the polarized light. A mathematic procedure, based on the evolution of the fluorescence anisotropy with the twisting angle of the films with respect to the excitation light, is used to evaluate the preferential orientation of R6G molecules in Lap films. The fluorescence method can be extended to study the preferential orientation of fluorescent molecules adsorbed in any organized rigid 2D system.