https://hdl.handle.net/10259/4364 2026-04-18T02:39:44Z https://hdl.handle.net/10259/11336 Non‐emissive RuII Polypyridyl Complexes as Efficient and Selective Photosensitizers for the Photooxidation of Benzylamines Yagüe Izquierdo, Cristina; Echevarría Poza, Igor; Vaquero Gutiérrez, Mónica; Fidalgo Zorrilla, Jairo; Carbayo Martín, Mª Aránzazu; Jalón Sotés, Félix Ángel; Lima, João C.; Moro, Artur J.; Manzano Manrique, Blanca Rosa; Espino Ordóñez, Gustavo Five new RuII polypyridyl complexes bearing N-(arylsulfonyl)-8-amidoquinolate ligands and three of their biscyclometalated IrIII congeners have been prepared and employed as photocatalysts (PCs) in the photooxidation of benzylamines with O2. In particular, the new RuII complexes do not exhibit photoluminescence, rather they harvest visible light efficiently and are very stable in solution under irradiation with blue light. Their non-emissive behavior has been related to the low electrochemical energy gaps and rationalized on the basis of theoretical calculations (DFT analysis) that predict low S0←T1 energy values. Moreover, the RuII complexes, despite being non-emissive, display excellent activities in the selective photocatalytic transformation of benzylamines into the corresponding imines. The presence of an electron-withdrawing group (-CF3) on the arene ring of the N-(arylsulfonyl)-8-amidoquinolate ligand improves the photocatalytic activity of the corresponding photocatalyst. Furthermore, all the experimental evidence, including transient absorption spectroscopy measurements suggest that singlet oxygen is the actual oxidant. The IrIII analogues are considerably more photosensitive and consequently less efficient photosensitizers (PSs). 2020-09-01T00:00:00Z https://hdl.handle.net/10259/11335 Advanced strategies in the design of Ir(III) biscyclometalated complexes for PDT Sanz Villafruela, Juan; Carbayo Martín, Mª Aránzazu; Martínez Alonso, Marta; Espino Ordóñez, Gustavo Photodynamic therapy (PDT) is a slightly invasive modality of chemotherapy that is arising as a new alternative for the clinical treatment of cancer and other illnesses. This therapy is based on the use of a photosensitiser (PS) which can be activated locally and specifically upon light irradiation to generate reactive oxygen species (ROS) which damage key biomolecules, leading to cancer cell death and tumour regression. This control in the cytotoxicity thanks to the activation of the PS, benefits from a reduction of the undesirable side-effects of the common chemotherapeutics. Among the wide variety of photosensitisers, Ir(III) complexes stand out due to their exceptional photophysical properties and high photostability. In the last years, there have been substantial advances in the development of new Ir(III) scaffolds that have allowed to overcome some of the limitations of PDT and might contribute to a wider clinical development. In this review, we feature the latest and cutting-edge strategies that have been recently employed in the design of new Ir(III) complexes to increase both their light harvesting ability in the therapeutic window and their photodynamic efficiency, to achieve a better biocompatibility, to increase the selectivity towards cancer cells or specific organelles and the possibility of using a combination of PDT with other advanced therapies to enhance the therapeutic effect. 2025-07-01T00:00:00Z https://hdl.handle.net/10259/11334 One-pot photocatalytic transformation of indolines into 3-thiocyanate indoles with new Ir(iii) photosensitizers bearing β-carbolines Sanz Villafruela, Juan; Martínez Alonso, Carmen; Echevarría Poza, Igor; Vaquero Gutiérrez, Mónica; Carbayo Martín, Mª Aránzazu; Fidalgo Zorrilla, Jairo; Rodríguez, Ana M.; Cuevas Vicario, José Vicente; Lima, João C.; Moro, Artur J.; Manzano Manrique, Blanca Rosa; Jalón Sotés, Félix Ángel; Espino Ordóñez, Gustavo Current societies demand sustainable synthetic procedures and accordingly the combination of two photocatalytic reactions in a one-pot process is a very appealing chemical tool. In the present work, we report on the development of new Ir(III) bis-cyclometallated photosensitizers with β-carboline ligands and disclose a simple and unprecedented photocatalytic one-pot two-step protocol for the chemoselective and C-3 regioselective oxidative thiocyanation of indolines to produce the corresponding 3-thiocyanato-indoles. The procedure is performed in THF at room temperature, in the presence of NH4SCN, O2 and the Ir(III) photocatalysts under blue light exposure. Moreover, this methodology combines important advantages such as an outstanding efficiency, based on good yields for low catalyst loadings, along with an excellent sustainability founded on the use of O2 as a green oxidant and light as the energy source. In addition, DFT studies have allowed a clear interpretation of the photophysical and electrochemical properties of the Ir(III) complexes and transient absorption experiments, along with other experimental proof, have demonstrated that the two photocatalytic processes are mediated by 1O2. Our results pave the way for future developments in the field of photocatalysis using Ir(III) biscyclometallated complexes as photosensitizers. 2021-01-01T00:00:00Z https://hdl.handle.net/10259/9756 Hybrid Hydroxyapatite–Metal Complex Materials Derived from Amino Acids and Nucleobases Jiménez Pérez, Alondra; Martínez Alonso, Marta; García Tojal, Javier Calcium phosphates (CaPs) and their substituted derivatives encompass a large number of compounds with a vast presence in nature that have aroused a great interest for decades. In particular, hydroxyapatite (HAp, Ca10(OH)2(PO4)6) is the most abundant CaP mineral and is significant in the biological world, at least in part due to being a major compound in bones and teeth. HAp exhibits excellent properties, such as safety, stability, hardness, biocompatibility, and osteoconductivity, among others. Even some of its drawbacks, such as its fragility, can be redirected thanks to another essential feature: its great versatility. This is based on the compound’s tendency to undergo substitutions of its constituent ions and to incorporate or anchor new molecules on its surface and pores. Thus, its affinity for biomolecules makes it an optimal compound for multiple applications, mainly, but not only, in biological and biomedical fields. The present review provides a chemical and structural context to explain the affinity of HAp for biomolecules such as proteins and nucleic acids to generate hybrid materials. A size-dependent criterium of increasing complexity is applied, ranging from amino acids/nucleobases to the corresponding macromolecules. The incorporation of metal ions or metal complexes into these functionalized compounds is also discussed. Artículo de revisión 2024-09-01T00:00:00Z