Person: Rodríguez Agarrabeitia, Antonia
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First Name
Antonia
Last Name
Rodríguez Agarrabeitia
Affiliation
Universidad Complutense de Madrid
Faculty / Institute
Óptica y Optometría
Department
Química Orgánica
Area
Química Orgánica
Identifiers
38 results
Search Results
Now showing 1 - 10 of 38
Item Circularly Polarized Luminescence by Visible-Light Absorption in a Chiral O-BODIPY Dye: Unprecedented Design of CPL Organic Molecules from Achiral Chromophores(Journal of the American Chemical Society, 2014) Márquez Sánchez-Carnerero, Esther María; Moreno Jiménez, Florencio; Lora Maroto, Beatriz; Rodríguez Agarrabeitia, Antonia; Ortíz García, María Josefa; Vo, Bryan G.; Muller, Gilles; Moya Cerero, Santiago de laCircularly polarized luminescence (CPL) in simple (small, nonaggregated, nonpolymeric) O-BODIPYs(R)-1 and (S)-1 by irradiation with visible light is first detected as proof of the ability of a new structural design to achieve CPL from inherently achiral monochromophore systems in simple organic molecules. The measured level of CPL (|glum|) in solution falls into the usual range of that obtained from other simple organic molecules (10−5−10−2range), but the latter having more complex architectures since axially chiral chromophores or multichromophore systems are usually required. The new design is based on chirally perturbing the acting achiral chromophore by orthogonally tethering a single axially chiral 1,1′-binaphtyl moiety to it. The latter does not participate as a chromophore in the light-absorption/emission phenom-enon. This simple design opens up new perspectives for the future development of new small-sized CPL organic dyes (e.g., those based on other highly luminescent achiral chromophores and/or chirally perturbing moieties), as well as for the improvement of the CPL properties of the organic molecules spanning their use in photonic applications.Item Generation of multiple triplet states in an orthogonal bodipy dimer: a breakthrough spectroscopic and theoretical approach(Physical chemistry chemical physics, 2022) García Moreno, Inmaculada; Postils, Verónica; Rebollar, Esther; Ortíz García, María Josefa; Rodríguez Agarrabeitia, Antonia; Casanova, DavidGeneration of triplet states in assemblies of organic chromophores is extremely appealing for their potential use in optoelectronic applications. In this work, we investigate the intricacies of triplet state generation in an orthogonal BODIPY dimer by combining delayed photoemission techniques with electronic structure calculations. Our analysis provides a deep understanding of the electronic states involved, and describes different competing deactivation channels beyond prompt radiative decay. In particular, we identify charge-transfer (CT) mediated intersystem crossing (ISC) as the most likely mechanism for the triplet state generation in this system. The different emission bands at long times can be associated with delayed fluorescence, CT emission and phosphorescence from multiple low-energy triplets. Interestingly, the dependence of the yield of triplet state population and emission profiles with the solvent polarity evidences the decisive role of the CT configuration in the fate of the photoactivated dimer, controlling the relative ISC, reverse ISC, and internal conversion efficiencies. Overall, the present results provide a rather complete description of the delayed photophysics in the BODIPY dimer, but are not able to fully rationalize the unexpected photoluminescence recorded at long wavelengths (≥ 900 nm). We hypothesize that the origin of this emission, not present in BODIPY monomers, emerges from intermonomer interactions triggered by intramolecular distortions opening up a new vision in the controverted mechanism driving the photophysical behavior from orthogonally linked organic monomers.Item Tailoring the Molecular Skeleton of Aza-BODIPYs to Design Photostable Red-Light-Emitting Laser Dyes(ChemPhotoChem, 2018) Prieto Castañeda, Alejandro; Avellanal Zaballa, Edurne; Gartzia Rivero, Leire; Cerdán Pedraza, Luis; Rodríguez Agarrabeitia, Antonia; García Moreno, Inmaculada; Bañuelos Prieto, Jorge; Ortíz García, María JosefaIn this article the design and characterization of a set of novel red‐light‐emitting laser aza‐BODIPY dyes is reported. The applied synthetic method allows an exhaustive and versatile functionalization of both the dipyrrin core and the boron bridge. From the analysis of the photophysical and laser signatures, we determine the suitable modifications of the chromophoric backbone necessary to modulate the emission spectral region, efficiency and photostability under a strong irradiation regime. These dyes are endowed with efficient fluorescence and laser emission, and are particularly outstanding in terms of their high photostability, a key parameter to guarantee long‐lasting emission in any (bio)technological application. The herein‐reported results support, for the first time, the viability of aza‐BODIPYs as tunable red laser dyes. In fact, the laser performances of some of the tested aza‐BODIPYs surpass those of commercially available laser dyes in the same spectral region.Item First Lanthanide Complex for de Novo Phasing in Native Protein Crystallography at 1 Å Radiation(ACS Applied Bio Materials, 2021) Prieto Castañeda, Alejandro; Martínez Caballero, Siseth; Rodríguez Agarrabeitia, Antonia; García Moreno, Inmaculada; Moya Cerero, Santiago de la; Ortíz García, María Josefa; Hermoso, Juan A.Phasing agents enabling de novo protein structure determination at ca. 1 Å, the wavelength corresponding to the maximum intensity of the synchrotron facilities applied in biomacromolecular crystallography, have been long sought-after. The first phasing agent designed for solving native protein structures at 0.97934 Å is described herein. The agent consists of a neutral ytterbium(III)-caged complex that exhibits higher anomalous signals at shorter wavelengths when compared to the best, currently applied lanthanide-based phasing agents, all of them based on gadolinium or terbium. As a proof of principle, the complex allows determining the 3D structure of a 36 kDa protein without setting the incident beam wavelength at the metal absorption edge, the strategy followed to date to gain the strongest anomalous signal even at the expense of crystallographic resolution. The agent becomes nondisruptive to the diffraction quality of the marked crystals and allows determining accurate phases, both leading to high-quality electron-density maps that enable the full tracing of the protein structure only with one agent unit bound to the protein. The high phasing power, efficient binding to the protein, low metal−macromolecule ratio, and easy handling support the developed Yb(III) complex as the best phasing agent for X-ray crystallography of a complex biomacromolecule without using modified analogues.Item Unprecedented induced axial chirality in a molecular BODIPY dye: strongly bisignated electronic circular dichroism in the visible region(Chemical Communications, 2013) Márquez Sánchez-Carnerero, Esther María; Moreno Jiménez, Florencio; Lora Maroto, Beatriz; Rodríguez Agarrabeitia, Antonia; Bañuelos Prieto, Jorge; Arbeloa, Teresa; López Arbeloa, Íñigo María; Ortíz García, María Josefa; Moya Cerero, Santiago de laEnantiomeric bis(BODIPYs) 1a and 1b exhibit strong bisignated ECD due to the formation of a stable helical conformation with induced axial chirality, which allows efficient excito coupling of the BODIPY chromophores in the Vis region.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; Ortíz 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 Singlet Fission Mediated Photophysics of BODIPY Dimers(Journal of physical chemistry letters, 2018) Montero, Raul; Martínez Martínez, Virginia; Longarte, Asier; Epelde Elezcano, Nerea; Palao Utiel, Eduardo; Lamas, Iker; Manzano, Hegoi; Rodríguez Agarrabeitia, Antonia; López Arbeloa, Íñigo María; Ortíz García, María Josefa; García Moreno, InmaculadaThe photodynamics of an orthogonal BODIPY dimer, particularly the formation of triplet states, has been explored by femtosecond and nanosecond transient absorption measurements. The short time scale data show the appearance of transient features of triplet character that, according to quantitative analysis of their intensities, account for more than 100% of the initially excited molecules, which reveals the occurrence of a singlet fission process in the isolated dimers. The formation rate of the triplet correlated state 1(TT) is found to depend on the solvent polarity, pointing to the mediation of a charge transfer character state. The dissociation of the 1(TT) state into pairs of individual triplets determines the triplet yield measured in the long time scales. The kinetic model derived from the results provides a comprehensive view of the photodynamics of BODIPY dimers and permits rationalization of the photophysical parameters of these systems.Item Mitochondria selective trackers for long-term imaging based on readily accessible neutral BODIPYs(Chemical Communications, 2021) Ramos Torres, Ágata; Avellanal Zaballa, Edurne; García Garrido, Fernando; Fernández Martínez, Ana B.; Prieto Castañeda, Alejandro; Rodríguez Agarrabeitia, Antonia; Bañuelos Prieto, Jorge; García Moreno, Inmaculada; Lucio Cazaña, Francisco Javier; Ortíz García, María JosefaWe report the design of a new model based on a small neutral 8-aryl-3-formylBODIPY and its suitability to develop privileged highly bright and photostable fluorescent probes for selective and, more importantly, covalent staining of mitochondria.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 Coumarin–BODIPY hybrids by heteroatom linkage: versatile, tunable and photostable dye lasers for UV irradiation(Physical Chemistry Chemical Physics, 2015) Esnal, Ixone; Duran-Sampedro, Gonzalo; Rodríguez Agarrabeitia, Antonia; Bañuelos, Jorge; García-Moreno, Inmaculada; Macías, Maria Ángeles ; Peña-Cabrera, Eduardo; López-Arbeloa, Iñigo; De la Moya, Santiago; Ortiz, Maria JoséLinking amino and hydroxycoumarins to BODIPYs through the amino or hydroxyl group lets the easy construction of unprecedented photostable coumarin–BODIPY hybrids with broadened and enhanced absorption in the UV spectral region, and outstanding wavelength-tunable laser action within the green-to-red spectral region (∼520–680 nm). These laser dyes allow the generation of a valuable tunable UV (∼260–350 nm) laser source by frequency doubling, which is essential to study accurately the photochemistry of biological molecules under solar irradiation. The tunability is achieved by selecting the substitution pattern of the hybrid. Key factors are the linking heteroatom (nitrogen vs. oxygen), the number of coumarin units joined to the BODIPY framework and the involved linking positions.