Person: Ortiz García, María Josefa
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First Name
María Josefa
Last Name
Ortiz García
Affiliation
Universidad Complutense de Madrid
Faculty / Institute
Ciencias Químicas
Department
Química Orgánica
Area
Química Orgánica
Identifiers
10 results
Search Results
Now showing 1 - 10 of 10
Item Carboxylates versus Fluorines: Boosting the Emission Properties of Commercial BODIPYs in Liquid and Solid Media(Advanced Functional Materials, 2013) Durán Sampedro, Gonzalo; Rodríguez Agarrabeitia, Antonia; Cerdán, Luis; Pérez Ojeda, María Eugenia; Costela, Angel; García‐Moreno, Inmaculada; Esnal, Ixone; Bañuelos, Jorge; López Arbeloa, Iñigo; Ortiz García, María JosefaA new and facile strategy for the development of photonic materials is presented that fufi lls the conditions of being effi cient, stable, and tunable laser emitters over the visible region of spectrum, with the possibility of being easily processable and cost-effective. This approach uses poly(methyl methacrylate) (PMMA) as a host for new dyes with improved effi ciency and photostability synthesized. Using a simple protocol, fl uorine atoms in the commercial (4,4-difl uoro-4-bora-3a,4a-diaza-s-indacene) ( F -BODIPY) by carboxylate groups. The new O -BODIPYs exhibit enhanced optical properties and laser behavior both in the liquid and solid phases compared to their commercial analogues. Lasing effi ciencies up to 2.6 times higher than those recorded for the commercial dyes are registered with high photostabilities since the laser output remain at 80% of the initial value after 100 000 pump pulses in the same position of the sample at a repetition rate of 30 Hz; the corresponding commercial dye entirely loses its laser action after only 12 000 pump pulses. Distributed feedback laser emission is demonstrated with organic fi lms incorporating new O -BODIPYs deposited onto quartz substrates engraved with appropriated periodical structures. These dyes exhibit laser thresholds up to two times lower than those of the corresponding parent dyes with lasing intensities up to one order of magnitude higher.Item Increased laser action in commercial dyes from fluorination regardless of their skeleton(Laser Physics Letters, 2014) Durán Sampedro, Gonzalo; Rodríguez Agarrabeitia, Antonia; Arbeloa Lopez, Teresa; Bañuelos, Jorge; López Arbeloa, Iñigo; Chiara, José Luis; Garcia Moreno, Inmaculada; Ortiz García, María JosefaThe direct and simple fluorination of representative organic laser dyes with emission covering the entire visible spectrum, from blue to red, including Coumarin 460, Pyrromethene 546, Rhodamine 6G and Perylene Red, enhances laser efficiencies by a factor up to 1.8 with respect to the corresponding non-fluorinated parent dyes. More importantly, fluorination also significantly enhances the photostability of the dyes, even under drastic laser pumping conditions.Item First Highly Efficient and Photostable and Derivatives of 4,4‐Difluoro‐4‐bora‐3a,4a‐diaza‐s‐indacene (BODIPY) as Dye Lasers in the Liquid Phase, Thin Films, and Solid‐State Rods(Chemistry Europe, 2014) Durán Sampedro, Gonzalo; Esnal, Ixone; Rodríguez Agarrabeitia, Antonia; Bañuelos Prieto, Jorge; Cerdán, Luis; García Moreno, Inmaculada; Costela, Angel; López Arbeloa, Iñigo; Ortiz García, María JosefaA new library of E- and C-4,4-difluoro-4-bora-3a,4adiaza-s-indacene (BODIPY) derivatives has been synthesized through a straightforward protocol from commercially available BODIPY complexes, and a systematic study of the photophysical properties and laser behavior related to the electronic properties of the B-substituent group (alkynyl, cyano, vinyl, aryl, and alkyl) has been carried out. The replacement of fluorine atoms by electron-withdrawing groups enhances the fluorescence response of the dye, whereas electrondonor groups diminish the fluorescence efficiency. As a consequence, these compounds exhibit enhanced laser action with respect to their parent dyes, both in liquid solution and in the solid phase, with lasing efficiencies under transversal pumping up to 73% in liquid solution and 53% in a solid matrix. The new dyes also showed enhanced photostability. In a solid matrix, the derivative of commercial dye PM597 that incorporated cyano groups at the boron center exhibited a very high lasing stability, with the laser emission remaining at the initial level after 100 000 pump pulses in the same position of the sample at a 10 Hz repetition rate. Distributed feedback laser emission was demonstrated with organic films that incorporated parent dye PM597 and its cyano derivative. The films were deposited onto quartz substrates engraved with appropriate periodical structures. The C derivative exhibited a laser threshold lower than that of the parent dye as well as lasing intensities up to three orders of magnitude higher.Item Negishi reaction in BODIPY dyes. Unprecedented alkylation by palladium-catalyzed C–C coupling in boron dipyrromethene derivatives(RSC Advances, 2014) Durán Sampedro, Gonzalo; Palao, Eduardo; Rodríguez Agarrabeitia, Antonia; Moya Cerero, Santiago De La; Boens, Noël; Ortiz García, María JosefaNegishi reactions of 3-halogen and 3,5-dihalogen substituted BODIPYs with different organozinc reagents are reported as the first examples of this valuable palladium-catalyzed C–C coupling reaction into the family of the BODIPY dyes. It is demonstrated that the Negishi coupling is especially useful for obtaining interesting alkylated BODIPYs, including synthetically-valuable asymmetrically-3,5-disubstituted BODIPYs.Item An asymmetric BODIPY triad with panchromatic absorption for high-performance red-edge laser emission(Chemmical Communications, 2015) Durán Sampedro, Gonzalo; Rodríguez Agarrabeitia, Antonia; Garcia-Moreno, Inmaculada ; Gartzia-Rivero, Leire; Bañuelos, Jorge; López-Arbeloa, Ínigo; Ortiz García, María Josefa; Moya Cerero, Santiago De LaA rational design of an unprecedented asym. 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.Item Rational molecular design enhancing the photonic performance of red-emitting perylene bisimide dyes(Physical Chemistry Chemical Physics, 2017) Avellanal Zaballa, Edurne; Durán Sampedro, Gonzalo; Prieto Castañeda, Alejandro; Rodríguez Agarrabeitia, Antonia; García Moreno, Inmaculada; López Arbeloa, Íñigo María; Bañuelos Prieto, Jorge; Ortiz García, María JosefaWe report the synthesis of novel multichromophoric organic architectures, where perylene red is decorated with BODIPY and/or hydroxycoumarin dyes acting as light harvesters and energy donors. The computationally-aided photophysical study of these molecular assemblies reveals a broadband absorption which, regardless of the excitation wavelength, leads solely to a bright red-edge emission from perylene bisimide after efficient intramolecular energy transfer hops. The increase of the absorbance of these molecular antennas at key pumping wavelengths enhances the laser action of the commercial perylene red. The herein applied strategy based on energy transfer dye lasers should boost the use of perylene-based dyes as active media for red-emitting lasers.Item Synthesis and functionalization of new polyhalogenated BODIPY dyes. Study of their photophysical properties and singlet oxygen generation(Tetrahedron, 2012) Ortiz García, María Josefa; Rodríguez Agarrabeitia, Antonia; Durán Sampedro, Gonzalo; Bañuelos Prieto, Jorge; Arbeloa Lopez, Teresa; Massad, Walter ; Montejano, Hernán ; García, Norman ; Lopez Arbeloa, IñigoA theoretical and experimental study on the iodination of BODIPY dyes with different degrees of substitution has been developed. Polyhalogenated BODIPYs synthesized in this work are the first examples of this type of dyes with more than two halogen atoms in the BODIPY core and they can be selectively functionalized. Surprisingly, the position in which halogen is attached has a marked effect in the photophysical properties and modulates the fluorescence capacity of the resulting BODIPY. These iodinated BODIPYs are efficient singlet oxygen generators.Item Exploring the Application of the Negishi Reaction of HaloBODIPYs: Generality, Regioselectivity, and Synthetic Utility in the Development of BODIPY Laser Dyes(Journal of Organic Chemistry, 2016) Palao Utiel, Eduardo; Durán Sampedro, Gonzalo; Moya Cerero, Santiago De La; Madrid, Miriam; García López, Carmen; Rodríguez Agarrabeitia, Antonia; Verbelen, Bram; Dehaen, Wim; Boens, Nöel; Ortiz García, María JosefaThe generality of the palladium-catalyzed C–C coupling Negishi reaction when applied to haloBODIPYs is demonstrated on the basis of selected starting BODIPYs, including polyhalogenated and/or asymmetrical systems, and organozinc reagents. This reaction is an interesting synthetic tool in BODIPY chemistry, mainly because it allows a valuable regioselective postfunctionalization of BODIPY chromophores with different functional groups. In this way, functional patterns that are difficult to obtain by other procedures (e.g., asymmetrically functionalized BODIPYs involving halogenated positions) can now be made. The regioselectivity is achieved by controlling the reaction conditions and is based on almost-general reactivity preferences, and the nature of the involved halogens and their positions. This ability is exemplified by the preparation of a series of new BODIPY dyes with unprecedented substitution patterns allowing noticeable lasing properties.Item A versatile fluorescent molecular probe endowed with singlet oxygen generation under white-light photosensitization(Dyes and Pigments, 2017) Durán Sampedro, Gonzalo; Epelde Elezcano, Nerea; Martínez Martínez, Virginia; Esnal Martínez, Ixone; Bañuelos Prieto, Jorge; García Moreno, Inmaculada; Rodríguez Agarrabeitia, Antonia; Moya Cerero, Santiago De La; Tabero Truchado, Andrea; Lázaro Carrillo, Ana; Villanueva Oroquieta, Ángeles; Ortiz García, María Josefa; López Arbeloa, Íñigo MaríaDespite fluorescent photodynamic therapy (fluorescent-PDT) dyes are promising theranostic agents, current approaches unfortunately involve crucial shortcomings (such as, narrow absorption bands, high cost, low bio-compatibility and specificity, low dual efficiency) making difficult their clinical translation. Particularly, efficient fluorescent-PDT agents triggered under white-light, with potential application in topic solar treatments, are scarce. Here, we describe the rational development of a novel fluorescent-PDT molecular biomaterial based on BODIPY building blocks able to sustain, simultaneously, synthetic accessibility, high fluorescence and phototoxicity within a broad spectral window, biocompatibility, including low dark toxicity and high cell permeability with selective accumulation in lysosomes and, what is more important, excellent efficient activity triggered under white light. These all-in-one combined properties make the new dye a valuable ground platform for the development of future smarter theranostic agents.Item Chlorinated BODIPYs: Surprisingly Efficient and Highly Photostable Laser Dyes(European Journal of Organic Chemistry, 2012) Durán Sampedro, Gonzalo; Rodríguez Agarrabeitia, Antonia; García Moreno, Inmaculada; Costela, Angel; Bañuelos, Jorge; Arbeloa, Teresa; López Arbeloa, Iñigo; Chiara, Jose Luis; Ortiz García, María JosefaA series of mono‐ to hexachlorinated BODIPY dyes have been prepared in good to excellent yields through the use of chlorosuccinimide as an inexpensive halogenating reagent. This library of chlorinated dyes allowed analysis in detail, from the experimental and theoretical points of view, of the dependency of the photophysical and optical properties of the dyes on the number and positions of the chlorine substituents on their BODIPY cores. Quantum mechanical calculations predict the regioselectivity of the halogenation reaction and explain why some positions are less prone to chlorination. The new chlorinated BODIPYs exhibit enhanced laser action with respect to their non‐halogenated analogues, both in liquid solution and in the solid phase. In addition, chlorination is a facile and essentially costless protocol for overcoming important shortcomings exhibited by commercially available BODIPYs, which should favor their practical applications in optical and sensing fields.