An asymmetric BODIPY triad with panchromatic absorption for high-performance red-edge laser emission

© The Royal Society of Chemistry 2015. A rational design of an unprecedented asymmetric cassette triad based entirely on BODIPY chromophores allows efficient light harvesting over the UV-vis spectral region, leading to a bright and stable red-edge laser emission via efficient energy-transfer processes.Peer Reviewe

Exploring BODIPY Derivatives as Singlet Oxygen Photosensitizers for PDT

This minireview is devoted to honoring the memory of Dr. Thomas Dougherty, a pioneer of modern photodynamic therapy (PDT). It compiles the most important inputs made by our research group since 2012 in the development of new photosensitizers based on BODIPY chromophore which, thanks to the rich BODIPY chemistry, allows a finely tuned design of the photophysical properties of this family of dyes to serve as efficient photosensitizers for the generation of singlet oxygen. These two factors, photophysical tuning and workable chemistry, have turned BODIPY chromophore as one of the most promising dyes for the development of improved photosensitizers for PDT. In this line, this minireview is mainly related to the establishment of chemical methods and structural designs for enabling efficient singlet oxygen generation in BODIPYs. The approaches include the incorporation of heavy atoms, such as halogens (iodine or bromine) in different number and positions on the BODIPY scaffold, and also transition metal atoms, by their complexation with Ir(III) center, for instance. On the other hand, low‐toxicity approaches, without involving heavy metals, have been developed by preparing several orthogonal BODIPY dimers with different substitution patterns. The advantages and drawbacks of all these diverse molecular designs based on BODIPY structural framework are described

Material híbrido fotoactivo, método de obtención y uso del material

La presente invención se refiere a un material híbrido fotoactivo que comprende al menos un colorante con propiedades fluorescentes y estructura de fórmula general (I) que representa una molécula aromática y sus formas resonantes: donde X es seleccionado entre CH o N e Y es seleccionado dentro del grupo compuesto por S, O, N, CH y NH; de tal forma que cuando X=CH, Y es seleccionada entre S, O, N, CH o NH, y cuando X=N, entonces Y=O; siendo n=+1 cuando Y=O, NH o S y n=0 cuando Y=N o CH; R1, R2, R3 y R4 pueden ser iguales o distintos entre sí y seleccionados entre: o N(R11)(R12),donde R11 y R12 son iguales o distintos entre sí y seleccionados dentro del grupo compuesto por: H, dicho colorante estando contenido y encapsulado por un material poroso cristalino de composición magnesioaluminofosfato (MgAPO) que se caracteriza por poseer poros con un primer diámetro comprendido en el intervalo de 4 a 7 , incluidos ambos límites, y un segundo diámetro comprendido en el intervalo de 4 a 7.5 incluidos ambos límites, que presenta un sistema de canales monodireccional delimitados por anillos de diez a doce átomos de Al y P en coordinación tetraédrica. Asimismo, la invención contempla un método de preparación del material híbrido definido anteriormente, así como las aplicaciones de dicho material híbridoPeer reviewedConsejo Superior de Investigaciones Científicas, Universidad del País Vasco Euskal Erriko UnibertsitateaB1 Patente sin examen previ

Singular laser behavior of hemicyanine dyes: Unsurpassed efficiency and finely structured spectrum in the near-IR region

In this paper we identify the origin of a novel and singular laser behavior of the hemicyanine dye LDS 722 transversally pumped at 532 nm. With lasing efficiencies as high as 43%, in spite of the fluorescence quantum yields being as low as 0.075, the laser spectra exhibit a finely structured spectral profile, with a periodic modulation with peak separation 0.4 nm, not related to mode selection due to spatial or spectral hole burning. The correlation of the LDS 722 lasing behavior as a function of both environmental properties (polarity, viscosity, protic character of the solvent) and pumping conditions (cavity configuration, pump geometry and energy) with its photophysical properties provides inklings to understand the physics responsible for the peculiar laser behavior in these rather complex dyes.Peer Reviewe

8-phenyl-substituted dipyrromethene center dot BF2 complexes as highly efficient and photostable laser dyes

We report oil the synthesis and the photophysical and lasing properties of two new dipyrromethene.BF2, dyes. analogues of the commercial dye PM567, dissolved in liquid solutions or ill polymeric matrices of poly(methyl methacrylate) and as solid copolymers with methyl methacrylate, where the chromophore is covalently bound to the polymeric chains. The new dyes have the 8 position substituted by the group p-(acetoxypolymetlylene)phenyl or p-(methacryloyloxypolymethylene)phenyl (number of methylenes = 1 or 3). Good correlations between the photophysical properties in dilute solutions and the lasing characteristics ill moderately concentrated solutions have been observed. The presence of the 8-phenyl substituent does not significantly modify the photophysics of the chromophore. Theoretical calculations were performed to rationalize this behavior. Under transversal pumping at 534 nm, laser efficiencies up to 46% were obtained for liquid Solutions, which were found to be nearly independent of the nature of the solvent and the length of the polymethylene chain. For solid samples, lasing efficiencies of up to 23% and good photostabilities, With 96% of the initial laser Output after 100 000 PUMP pulses at 10 Hz, were established.Peer reviewe

One-dimensional antenna systems by crystallization inclusion of dyes (One-Pot Synthesis) within zeolitic MgAPO-36 nanochannels

The nanopores of magnesium aluminophosphate MgAPO-36 (ATS structure) favor the formation of J-type aggregates in dyes with a general molecular skeleton of three fused aromatic rings. The particular distribution of these J-aggregate species and monomers, in a practically collinear disposition along the 1D-channels, allows an efficient transfer of electronic energy by dipole-dipole interaction. In order to achieve a material susceptible to be used as an artificial photonic antenna, covering a broader range of the UV-vis light spectrum and available by one-pot synthesis, the fluorescing dye acridine (AC) is occluded for the first time within MgAPO-36, both alone and with different ratios of the fluorescing dye Pyronine Y (PY). The one-dimensional energy-transfer process between the different chromophores and between the monomers and their red-shifted J-aggregates is controlled by the total concentration of dyes and their relative AC:PY ratio in the matrix. In the optimized AC:PY concentrations, the wavelength range antenna action is extended from near-UV to about 700 nm, transporting the light energy through the whole visible spectrum (blue to green to red) and spatially, from end to the end of the crystals. © 2013 American Chemical Society.This work was funded by the Basque Government (IT339-10, S-12UN-140, and S-13UN) and the Spanish Ministerio de Economıa y Competitividad, MICINN (MAT2012-31127). V.M.M. and R.S.L. acknowledge Ministerio de Economía y Competitividad for Ramón y Cajal (RYC-2011-0955) and Universidad del País Vasco (UPV-EHU) for their respective contract and fellowship.Peer Reviewe

One-dimensional antenna systems by crystallization inclusion of dyes (One-Pot Synthesis) within zeolitic MgAPO-36 nanochannels

The nanopores of magnesium aluminophosphate MgAPO-36 (ATS structure) favor the formation of J-type aggregates in dyes with a general molecular skeleton of three fused aromatic rings. The particular distribution of these J-aggregate species and monomers, in a practically collinear disposition along the 1D-channels, allows an efficient transfer of electronic energy by dipole-dipole interaction. In order to achieve a material susceptible to be used as an artificial photonic antenna, covering a broader range of the UV-vis light spectrum and available by one-pot synthesis, the fluorescing dye acridine (AC) is occluded for the first time within MgAPO-36, both alone and with different ratios of the fluorescing dye Pyronine Y (PY). The one-dimensional energy-transfer process between the different chromophores and between the monomers and their red-shifted J-aggregates is controlled by the total concentration of dyes and their relative AC:PY ratio in the matrix. In the optimized AC:PY concentrations, the wavelength range antenna action is extended from near-UV to about 700 nm, transporting the light energy through the whole visible spectrum (blue to green to red) and spatially, from end to the end of the crystals. © 2013 American Chemical Society.This work was funded by the Basque Government (IT339-10, S-12UN-140, and S-13UN) and the Spanish Ministerio de Economıa y Competitividad, MICINN (MAT2012-31127). V.M.M. and R.S.L. acknowledge Ministerio de Economía y Competitividad for Ramón y Cajal (RYC-2011-0955) and Universidad del País Vasco (UPV-EHU) for their respective contract and fellowship.Peer Reviewe

Modulating dye aggregation by incorporation into 1D-MgAPO nanochannels

The fluorescing dye Pyronine Y has been incorporated by crystallization inclusion into three different one‐dimensional microporous aluminophosphate host materials. A computer‐aided rational choice of the framework of the host material made it possible to modulate the aggregation state of the guest dye molecules. Undesirable H‐type dimers of Pyronine Y are included within the large channels of the AFI structure, which allow the inclusion of any of the aggregated species of the dye. Density functional theory (DFT) calculations show that H‐type aggregate formation is suppressed within the ATS framework. Experimental results indicate that red‐emissive J‐type aggregates are formed instead, offering a one‐directional, organized, multicolour emission system that is interesting for energy transport. Complete suppression of aggregation is achieved by the inclusion of Pyronine Y within the AEL‐type structure, due to its particular topology and channel dimensions This results in a highly fluorescent hybrid system with extraordinarily preferential alignment of the chromophores. Here, we report experimental evidence and modelling insights for how the “cage effect” of the nanochannels can tune the optical properties of the hybrid composite material by influencing the aggregation state of the dye.This work was funded by the Spanish Ministerio de Economia y Competitividad, MICINN (MAT 2010–20646‐C04–04), the Basque Government (IT339–10) and the European Research Council, under the Marie Curie Career Integration Grant program (FP7‐PEOPLE‐2011‐CIG), Grant Agreement PCIG09‐GA‐2011–291877. VMM and LGH acknowledge Ministerio de Economía y Competitividad for Ramón y Cajal (RYC‐2011–09505) and Juan de la Cierva contracts.Peer Reviewe

Anisotropic fluorescence materials: Effect of the synthesis conditions over the incorporation, alignment and aggregation of Pyronine y within MgAPO-5

In order to prepare a highly fluorescent anisotropic material, different hydrothermal synthesis conditions have been studied in an attempt to favor the incorporation of the fluorescing dye Pyronine Y as monomeric species within the large-pore nanoporous aluminophosphate MgAPO-5 (AFI-type structure) during its crystallization (one-pot synthesis). Valuable information regarding the dye orientation, molecular distribution and aggregation behaviour inside the nanochannels of MgAPO-5 as a function of the gel composition has been obtained using the FLIM technique (Fluorescence Lifetime Imaging Microscopy). DFT-based calculations of the different dye species occluded within the nanochannels of MgAPO-5 allowed us to explain the properties of the newly synthesised composite materials. Our results show that although H-aggregates can fit within the MgAPO-5 channels, their presence can be reduced by varying the synthesis parameters, in particular by decreasing the template and PY concentration and increasing Mg content.We are thankful for the financial support of the Spanish Ministry of Science and Innovation MICINN, Project MAT-2009-13569; the European Research Council, under the Marie Curie Career Integration Grant program (FP7-PEOPLE-2011-CIG), Grant Agreement PCIG09-GA-2011-291877; and Industry Program from the Basque Government: Saiotek project (S-PE10UN65, S-PE11UN64 and S-PE12UN140). LGH acknowledges Ministerio de Economía y Competitividad for a Juan de la Cierva contract and VMM for Gobierno Vasco IT339-10 (2012) contracts.Peer Reviewe