Person: Durán Sampedro, Gonzalo
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First Name
Gonzalo
Last Name
Durán Sampedro
Affiliation
Universidad Complutense de Madrid
Faculty / Institute
Ciencias Químicas
Department
Química Orgánica
Area
Química Orgánica
Identifiers
17 results
Search Results
Now showing 1 - 10 of 17
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 Annulative π-extension of BODIPYs made easy via gold(i)-catalyzed cycloisomerization(Chemical Science, 2020) Labella, Jorge; Durán Sampedro, Gonzalo; Martínez-Díaz, María Victoria; Torres, TomásHere we report gold(i)-catalyzed cycloisomerization as a new powerful synthetic tool for the preparation of pi-extended BODIPY derivatives. The catalytic system (PPh3AuCl)-Au-F/AgSbF(6)enables the synthesis of [b]-[2,1]naphtho-fused-BODIPYs (2a-2c) under mild conditions, in excellent yields and short reaction times. The reaction is totally regioselective to the 6-endo-dig product and for the alpha-position of the BODIPY, which is both the kinetically and thermodynamically favored pathway, as supported by the free energy profile calculated by means of Density Functional Theory (DFT). Moreover, this methodology also allows the synthesis of two new families of [b]-aryl-fused-BODIPYs, namely, [3,4]phenanthro- (2eand2f) and [1,2]naphtho-fused (2g) BODIPYs. Their molecular and electronic structures were established by NMR and UV-vis spectroscopies as well as single-crystal X-ray diffraction analysis. As can be noted from the X-ray structures,2a,2eand2gpresent interesting structural differences at both the molecular and packing level. Interestingly, despite being isomers, the UV/vis spectra of2aand2grevealed significant differences in their electronic structures. The origin of this finding was studied by Time-Dependent DFT calculations. Calculated DFT Nuclear Independent Chemical Shift (NICS(0)) values also supported the different electronic structures of2aand2g.Item New perylene-doped polymeric thin films for efficient and long-lasting lasers(Journal Of Materials Chemistry, 2012) Cerdán, Luis; Costela, Angel; Durán Sampedro, Gonzalo; García-Moreno, Inmaculada; Calle, Mariola; Juan-y-Seva, Marta; Abajo, Javier de; Turnbull, Graham A.An efficient strategy was established to optimize the performance of dye-doped host materials consisting of analyzing in a systematic way the dependence of their amplified spontaneous emission (ASE) efficiency and photostability on the composition and structure of the matrixes, selected to specifically avoid the thermal and/or chem. (photooxidation) processes, main mechanisms of dye photodegradation A number of exptl. polyimides were chosen as a host matrix and their behavior was compared with that of PMMA. The optical properties were correlated with the O permeation and thermal properties of the different polymeric hosts doped with perylene dyes to deepen the understanding of the photodegradation mechanism predominant in these dyes and to minimize its influence. High efficiency and photostable ASE from waveguides based on polymeric materials doped with Perylene Orange (PO), Perylene Red (PR), and mixtures of both are demonstrated. This enhancement in the optical properties allows reaching high gain and long-lasting distributed feedback (DFB) laser emission based on PO-doped polymer matrixes, even when operating in an unoptimized resonator.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 Double click macrocyclization with Sondheimer diyne of aza-dipyrrins for B–Free bioorthogonal imaging(Chemical Communications, 2023) Wu, Dan; Durán Sampedro, Gonzalo; Fitzgerald, Sheila; Garre, Massimiliano; O'Shea, DonalSequential azide/diyne cycloadditions proved highly effective for the macrocyclization of a bis-azido aza-dipyrrin. Macrocyclic aza-dipyrrin could be produced in 30 min at rt in water with changes in fluorescence intensity and lifetimes measurable upon reaction. Live cell microscopy showed that aza-dipyrrins were suitable for confocal and STED super-resolution imaging and a bioorthogonal response to macrocyclization could be detected in cellular compartments. These results will encourage a broader examination of the sensing and imaging uses of aza-dipyrrins.Item Anthracene‐Fused Oligo‐BODIPYs: A New Class of π‐Extended NIR‐Absorbing Materials(Angewandte Chemie International Edition, 2022) Labella, Jorge; Durán Sampedro, Gonzalo; Krishna, Swathi; Martínez‐Díaz, Victoria; Guldi, Dirk ; Torres, TomásLarge π‐conjugated systems are key in the area of molecular materials. Herein, we prepare via Au‐catalyzed cyclization a series of fully π‐conjugated anthracene‐fused oligo‐BODIPYs. Their structural and optoelectronic properties were studied by several techniques, ranging from X‐ray, UV/Vis, and cyclic voltammetry to transient absorption spectroscopy. As a complement, their electronic structures were explored by means of Density Functional Theory (DFT) calculations. Depending on the size and shape of the π‐conjugated skeleton, unique features—such as face‐to‐face supramolecular organization, NIR absorption and fluorescence as well as strong electron accepting character—were noted. All in all, the aforementioned features render them valuable for technological applications.Item A DIE responsive NIR-fluorescent cell membrane probe(Biochimica et Biophysica Acta (BBA) - Biomembranes, 2018) Wu, Dan; Cheung, Shane; Durán Sampedro, Gonzalo; Chen, Zhi-Long; Cahill, Ronan ; O'Shea, DonalIt is challenging to achieve selective off to on modulation of the emissive state of a fluorophore within a complex and heterogeneous cellular environment. Herein we show that the dis-assembly of a non-fluorescent aggregate to produce individual fluorescent molecules, termed disaggregation induced emission (DIE), can be utilised to achieve this goal with an amphiphilic BF2-azadipyrromethene (NIR-AZA) probe. Optical near-infrared properties of the NIR-AZA probe used in this study include absorption and emission maxima at 700 and 726 nm respectively when in the emissive non-aggregated state. Key to the success of the probe is the bis-sulfonic acid substitution of the NIR-AZA fluorophore, which is atypical for membrane probes as it does not contain zwitterionic lipid substituents. The aggregation/disaggregation properties of the NIR-fluorophore have been investigated in model surfactant and synthetic liposomal systems and shown to be emissive responsive to both. Real-time live cell imaging experiments in HeLa Kyoto and MC3T3 cells showed a rapid switch on of emission specific to the plasma membrane of viable and apoptotic cells attributable to a disaggregation-induced emission of the probe. Image analysis software confirmed localisation of fluorescence to the plasma membrane. Cell membrane staining was also effective for formaldehyde fixed cells, with staining possible either before or after fixation. This study adds new and important findings to recent developments of DIE responsive probes and further applications of this controllable emission-switching event are anticipated.Item Synthesis and properties of water-soluble 1,9-dialkyl-substituted BF2 azadipyrromethene fluorophores(Frontiers of Chemical Science and Engineering, 2019) Wu, Dan; Durán Sampedro, Gonzalo; O’Shea, DonalBis-alkylsulfonic acid and polyethylene glycol (PEG)-substituted BF2 azadipyrromethenes have been synthesized by an adaptable and versatile route. Only four synthetic stages were required to produce the penultimate fluorophore compounds, containing either two alcohol or two terminal alkyne substituents. The final synthetic step introduced either sulfonic acid or polyethylene glycol groups to impart aqueous solubility. Sulfonic acid groups were introduced by reaction of the bis-alcohol-substituted fluorophore with sulfur trioxide, and a double Cu(I)-catalyzed cycloaddition reaction between the bis-alkyne fluorophore and methoxypolyethylene glycol azide yielded a neutral bis-pegylated derivative. Both fluorophores exhibited excellent near-infrared (NIR) photophysical properties in methanol and aqueous solutions. Live cell microscopy imaging revealed efficient uptake and intracellular labelling of cells for both fluorophores. Their simple synthesis, with potential for last-step structural modifications, makes the present NIR-active azadipyrromethene derivatives potentially useful as NIR fluorescence imaging probes for live cells.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.