Person: Moreno Jiménez, Florencio
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First Name
Florencio
Last Name
Moreno Jiménez
Affiliation
Universidad Complutense de Madrid
Faculty / Institute
Óptica y Optometría
Department
Química Orgánica
Area
Química Orgánica
Identifiers
6 results
Search Results
Now showing 1 - 6 of 6
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; Ortiz 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 Dissimilar-at-boron N-BODIPYs: from light-harvesting multichromophoric arrays to CPL-bright chiral-at-boron BODIPYs(Organic Chemistry Frontiers, 2023) Ray, César; Avellanal-Zaballa, Edurne; Muñoz Úbeda, Mónica; Colligan, Jessica; Moreno Jiménez, Florencio; Muller, Gilles ; López Montero, Iván; Bañuelos, Jorge; Lora Maroto, Beatriz; Moya Cerero, Santiago De LaWe report a workable and easy approach for the direct post-multifunctionalization of common BODIPYs (F-BODIPYs) with minimal interference to the starting photophysical behavior. It entails the easy transformation of an F-BODIPY into the corresponding N-BODIPY by using a dissimilarly-N,N′-disubstituted bis(sulfonamide), which is easily obtained from ethane-1,2-diamine. This approach is exemplified by the rapid synthesis of a selected battery of unprecedented dissimilar-at-boron N-BODIPYs, which are rationally designed to act as efficient multichromophoric arrays for light harvesting by excitation energy transfer, as specific bioprobes for fluorescent imaging, or as efficient chiroptical dyes exhibiting visible circular dichroism and circularly polarized luminescence. Noticeably, this approach has led to the synthesis of the first CPL-bright chiral-at-boron BODIPYs, a significant novelty in BODIPY chemistry and CPL emittersItem Photochemical Oxidation of Thioketones by Singlet Molecular Oxygen Revisited: Insights into Photoproducts, Kinetics, and Reaction Mechanism(Journal of organic chemistry, 2015) Sánchez Arroyo, Antonio José; Pardo Botero, Zulay D.; Moreno Jiménez, Florencio; Herrera Fernández, Antonio; Martín, Nazario; García Fresnadillo, DavidPhotosensitized oxidation of trimethyl[2.2.1]-bicycloheptane thioketones by 1 O2 can yield more photoproducts than exclusively ketones and sulfines. Moreover, the ketone/sulfine ratio can be reversed when protic conditions and high thioketone concentrations are used, conversely to earlier results reporting ketones as the main photoproducts. A new mechanistic proposal for sulfine formation is suggested following intermolecular oxygen transfer from a peroxythiocarbonyl intermediate to a second thioketone molecule. Reaction quantum yields (10−5−10−2) depend on the reaction conditions and time. Sulfine production reaches a maximum at short irradiation times, whereas decomposition to the corresponding ketone is observed at long reaction times. When the thioketone substrate has a hydrogen atom at the α position a peroxyvinylsulfenic acid intermediate can be formed by proton transfer. Reaction of this intermediate with another thioketone molecule can yield more sulfine and its tautomeric vinylsulfenic acid, which dimerizes in situ to the thiosulfinate. The hydroperoxyl group of the peroxyvinylsulfenic acid can also rearrange to the α position, and by reaction with the starting thioketone, α-hydroxy thioketone and additional sulfine can be formed, while dehydration yields the α-oxo thioketone. In situ [2 + 2] and [4 + 2] self-cycloaddition of the α-oxo thioketone yields significant amounts of the corresponding adducts at prolonged irradiation times.Item Manipulating Charge-TransferStates in BODIPYs: A ModelStrategy to Rapidly Develop Photodynamic Theragnostic Agents(Chemistry: a european journal, 2020) Jiménez González, Josué; Prieto Montero, Ruth; Lora Maroto, Beatriz; Moreno Jiménez, Florencio; Ortiz García, María Josefa; Oliden Sánchez, Ainhoa; López Arbeloa, Íñigo María; Martínez Martínez, Virginia; Moya Cerero, Santiago De LaOn the basis of a family of BINOL (1,1′-bi-2-naphthol)-based O-BODIPY (dioxyboron dipyrromethene) dyes, it is demonstrated that chemical manipulation of the chromophoric push–pull character, by playing with the electron-donating capability of the BINOL moiety (BINOL versus 3,3'-dibromoBINOL) and with the electron-acceptor ability of the BODIPY core (alkyl substitution degree), is a workable strategy to finely balance fluorescence (singlet-state emitting action) versus the capability to photogenerate cytotoxic reactive oxygen species (triplet-state photosensitizing action). It is also shown that the promotion of a suitable charge-transfer character in the involved chromophore upon excitation enhances the probability of an intersystem crossing phenomenon, which is required to populate the triple state enabling singlet oxygen production. The reported strategy opens up new perspectives for rapid development of smarter agents for photodynamic theragnosis, including heavy-atom-free agents, from a selected organic fluorophore precursor.Item Electron ionization-induced fragmentation of bridgehead-substituted norbornan-2-ones derived from fenchone(International journal of mass spectrometry, 2012) Teso Vilar, Enrique; García Martínez, Antonio; García Fraile, Amelia; Moya Cerero, Santiago De La; Martínez Ruiz, María Paloma; Moreno Jiménez, FlorencioCamphor- and fenchone-based bridgehead-substituted norbornan-2-ones constitute an interesting class of chiral synthons with applications in stereoselective synthesis, due to the wide variety of stereo-controlled transformations which they can undergo. Despite their synthetic value, few mass spectral studies have been realized for these compounds due to the lack of general procedures for their preparation. In this paper we have carried out an electron ionization (EI) mass spectral study of a series of heteroatomically bridgehead-substituted 7,7-dimethylnorbornan-2-ones. Their cleavage mechanisms have been rationalized on the basis of the substituent shifts, as well as on the identification of relevant peaks through accurate mass measurements and collision-induced dissociation (CID) tandem mass-spectrometric experiments. The driving force for the main fragmentation pathways of C(1)-O- and C(1)-N-substituted 7,7-dimethylnorbornan-2-ones is the alpha-cleavage of the C(1) C(2) bond directed by the bridgehead substituent. Further rearrangements and fragmentations of the distonic ions initially formed lead to the major ions in the spectra of all the compounds. A comparison with the known behaviour of their isomeric 3,3-dimethylnorbornan-2-ones reveals that the key bridgehead heteroatom effect controlling the fragmentation pathways can be modulated by the position of the gem-dimethyl group. As a consequence, the corresponding fragmentation patterns of both isomeric series are very different. In contrast, the fragmentation patterns of 7,7-dimethyl-2-oxo-norbornanesulphonamides, whose main fragmentation pathway involves homolytic S N bond cleavage, are almost identical to those displayed by their 3,3-dimethylated isomersItem Spiranic BODIPYs: a ground-breaking design to improve the energy transfer in molecular cassettes(Chemical Communications, 2014) Márquez Sánchez-Carnerero, Esther María; Gartzia-Rivero, Leire; Moreno Jiménez, Florencio; Lora Maroto, Beatriz; Rodríguez Agarrabeitia, Antonia; Ortiz García, María Josefa; Bañuelos Prieto, Jorge; López Arbeloa, Íñigo María; Moya Cerero, Santiago De LaBoosted excitation energy transfer in spiranic O BODIPY/polyarenecassettes, when compared with the parent non-spiranic (flexible) system, is highlighted as a proof for the ability of a new structural design to improve the energy transfer in molecular cassettes