2026-06-08T01:05:52Zhttps://docta.ucm.es/rest/oai/request
oai:docta.ucm.es:20.500.14352/924842025-09-02T12:35:49Zcom_20.500.14352_14col_20.500.14352_15
Docta Complutense author Díaz Norambuena, Carolina author Avellanal Zaballa, Edurne author Prieto Castañeda, Alejandro author Bañuelos, Jorge author Moya Cerero, Santiago de la author Rodríguez Agarrabeitia, Antonia author Ortiz, María J. 2024-01-11T10:56:18Z 2024-01-11T10:56:18Z 2023 Díaz-Norambuena, C.; Avellanal-Zaballa, E.; Prieto-Castañeda, A.; Bañuelos, J.; de la Moya, S.; Agarrabeitia, A.R.; Ortiz, M.J. Formylation as a Chemical Tool to Modulate the Performance of Photosensitizers Based on Boron Dipyrromethene Dimers. Int. J. Mol. Sci. 2023, 24, 11837. h 1661-6596 10.3390/ijms241411837 https://hdl.handle.net/20.500.14352/92484 https://doi.org/10.3390/ijms241411837 https://www.mdpi.com/1422-0067/24/14/11837 Heavy-atom-free photosensitizers are envisioned as the next generation of photoactive molecules for photo-theragnosis. In this approach, and after suitable irradiation, a single molecular scaffold is able to visualize and kill tumour cells by fluorescence signalling and photodynamic therapy (PDT), respectively, with minimal side effects. In this regard, BODIPY-based orthogonal dimers have irrupted as suitable candidates for this aim. Herein, we analyse the photophysical properties of a set of formyl-functionalized BODIPY dimers to ascertain their suitability as fluorescent photosensitizers. The conducted computationally aided spectroscopic study determined that the fluorescence/singlet oxygen generation dual performance of these valuable BODIPY dimers not only depends on the BODIPY-BODIPY linkage and the steric hindrance around it, but also can be modulated by proper formyl functionalization at specific chromophoric positions. Thus, we propose regioselective formylation as an effective tool to modulate such a delicate photonic balance in BODIPY-based dimeric photosensitizers. The taming of the excited-state dynamics, in particular intramolecular charge transfer as the key underlying process mediating fluorescence deactivation vs. intersystem crossing increasing, could serve to increase fluorescence for brighter bioimaging, enhance the generation of singlet oxygen for killing activity, or balance both for photo-theragnosis. eng Attribution 4.0 International Formylation as a Chemical Tool to Modulate the Performance of Photosensitizers Based on Boron Dipyrromethene Dimers journal article UGFyYSBxdWUgZWwgcmVwb3NpdG9yaW8gaW5zdGl0dWNpb25hbCBkZSBsYSBVbml2ZXJzaWRhZCBkZSBNYWRyaWQgcHVlZGEgYWxtYWNlbmFyIHkgZGlzdHJpYnVpciBlbCBvYmpldG8gZGlnaXRhbCBkZXBvc2l0YWRvLCBlcyBuZWNlc2FyaW8gcXVlIGxhIHBlcnNvbmEgcXVlIGhhZ2EgZWwgZGVww7NzaXRvIGxlYSB5IGFjZXB0ZSBsYXMgY29uZGljaW9uZXMgZXN0YWJsZWNpZGFzIGVuIGVzdGEgbGljZW5jaWE6CuKAoiBBY2VwdGFuZG8gZXN0YSBsaWNlbmNpYSwgdXN0ZWQgY29tbyBhdXRvci9yZXMgeS9vIHByb3BpZXRhcmlvL3MgZGUgbG9zIGRlcmVjaG9zIGRlIHByb3BpZWRhZCBpbnRlbGVjdHVhbCwgb3RvcmdhIGFsIHJlcG9zaXRvcmlvIGRlIGxhIFVuaXZlcnNpZGFkIENvbXBsdXRlbnNlIGRlIE1hZHJpZCBlbCBkZXJlY2hvIG5vIGV4Y2x1c2l2byBkZSByZXByb2R1Y2Npw7NuIHkgZGlzdHJpYnVjacOzbiBkZSBzdSBvYnJhIGVuIGN1YWxxdWllciBmb3JtYXRvIHkgbWVkaW8uCuKAoiBFbCBkZXBvc2l0YW50ZSwgZW4gY2FzbyBkZSB1bmEgb2JyYSBjb24gbcOhcyBkZSB1biBhdXRvciwgZ2FyYW50aXphIHF1ZSBsbyBoYWNlIHJlc3BvbnNhYmxlbWVudGUgZW4gbm9tYnJlIHkgY29uIGNvbnNlbnRpbWllbnRvIGRlIGxvcyBkZW3DoXMgYXV0b3Jlcy4K4oCiIEFjZXB0YSBxdWUgZWwgcmVwb3NpdG9yaW8gZGUgbGEgVW5pdmVyc2lkYWQgQ29tcGx1dGVuc2UgZGUgTWFkcmlkIHB1ZWRhIGNvbnNlcnZhciBtw6FzIGRlIHVuYSBjb3BpYSBkZSBlc3RlIGRvY3VtZW50byB5LCBzaW4gYWx0ZXJhciBzdSBjb250ZW5pZG8sIGNvbnZlcnRpcmxvIGEgY3VhbHF1aWVyIGZvcm1hdG8gZGUgZmljaGVybywgbWVkaW8gbyBzb3BvcnRlLCBwYXJhIHByb3DDs3NpdG9zIGRlIHNlZ3VyaWRhZCB5IHByZXNlcnZhY2nDs24uCuKAoiBEZWNsYXJhIHF1ZSBlbCBkb2N1bWVudG8gZXMgdW4gdHJhYmFqbyBvcmlnaW5hbCBzdXlvIHkgcXVlIGN1ZW50YSBjb24gbGEgcG9zdGVzdGFkIHBhcmEgb3RvcmdhciBsb3MgZGVyZWNob3MgY29udGVuaWRvcyBlbiBlc3RhIGxpY2VuY2lhLiBUYW1iacOpbiBkZWNsYXJhIHF1ZSBzdSBkb2N1bWVudG8gbm8gaW5mcmluZ2UgbG8gZXN0YWJsZWNpZG8gZW4gbGEgdmlnZW50ZSBsZWdpc2xhY2nDs24gZGUgcHJvcGllZGFkIGludGVsZWN0dWFsLgrigKIgU2kgZWwgZG9jdW1lbnRvIGNvbnRpZW5lIG1hdGVyaWFsZXMgZGUgbG9zIGN1YWxlcyBubyB0aWVuZSBsb3MgZGVyZWNob3MgZGUgYXV0b3IsIGRlY2xhcmEgcXVlIGhhIG9idGVuaWRvIGVsIHBlcm1pc28gc2luIHJlc3RyaWNjacOzbiBkZWwgcHJvcGlldGFyaW8gcGFyYSBvdG9yZ2FyIGEgbGEgVW5pdmVyc2lkYWQgQ29tcGx1dGVuc2UgZGUgTWFkcmlkIGxvcyBkZXJlY2hvcyByZXF1ZXJpZG9zIHBvciBlc3RhIGxpY2VuY2lhLCB5IHF1ZSBlc2UgbWF0ZXJpYWwsIGN1eW9zIGRlcmVjaG9zIHNvbiBkZSB0ZXJjZXJvcywgZXN0w6EgY2xhcmFtZW50ZSBpZGVudGlmaWNhZG8geSByZWNvbm9jaWRvIGRlbnRybyBkZWwgY2NvbnRlbmlkbyBkZWwgZG9jdW1lbnRvLgrigKIgU2kgZWwgZG9jdW1lbnRvIHNlIGJhc2EgZW4gdW5hIG9icmEgcXVlIGhhIHNpZG8gcGF0cm9jaW5hZGEgbyBhcG95YWRhIHBvciB1bmEgYWdlbmNpYSB1IG9yZ2FuaXphY2nDs24gZGlmZXJlbnRlIGRlIGxhIFVuaXZlcnNpZGFkIENvbXBsdXRlbnNlIGRlIE1hZHJpZCwgdXN0ZWQgZGVjbGFyYSBxdWUgaGEgY3VtcGxpZG8gY29uIGxhcyBvYmxpZ2FjaW9uZXMgcmVxdWVyaWRhcyBwb3IgZXN0ZSBjb250cmF0byBvIGFjdWVyZG8uCuKAoiBMYSBVbml2ZXJzaWRhZCBDb21wbHV0ZW5zZSBkZSBNYWRyaWQgaWRlbnRpZmljYXLDoSBjbGFyYW1lbnRlIHN1L3Mgbm9tYnJlL3MgY29tbyBlbC9sb3MgYXV0b3IvZXMgbyBwcm9waWV0YXJpby9zIGRlIGxvcyBkZXJlY2hvcyBkZWwgZG9jdW1lbnRvLCB5IG5vIGhhcsOhIG5pbmd1bmEgYWx0ZXJhY2nDs24gZGUgc3UgZG9jdW1lbnRvIGRpZmVyZW50ZSBhIGxhcyBwZXJtaXRpZGFzIGVuIGVzdGEgbGljZW5jaWEuCuKAoiBUcmFiYWpvcyBkZXBvc2l0YWRvcyBwb3Igc3UgcHJvcGlvIGF1dG9yOiBhbCBhdXRvLWFyY2hpdmFyIGVzdGEgY29sZWNjacOzbiBkZSBmaWNoZXJvcyB5IG1ldGFkYXRvcyBiaWJsaW9ncsOhZmljb3MgYXNvY2lhZG9zLCBvdHJvZ28sIGFsIHJlcG9zaXRvcmlvIGluc3RpdHVjaW9uYWwgZGUgbGEgVW5pdmVyc2lkYWQgQ29tcGx1dGVuc2UgZGUgTWFkcmlkIGVsIGRlcmVjaG8gcGFyYSBhbG1hY2VuYXJsb3MgeSBkaXN0cmlidWlybG9zLiBEZWNsYXJvIHF1ZSBlc3RlIG1hdGVyaWFsIGVzIGRlIG1pIHByb3BpZWRhZCBpbnRlbGVjdHVhbCB5IHF1ZSBlbCByZXBvc2l0b3JpbyBpbnN0aXR1dGljaW9uYWwgZGUgbGEgVW5pdmVyc2lkYWQgQ29tcGx1dGVuc2UgZGUgTWFkcmlkLCBubyBhc3VtZSByZXNwb25zYWJpbGlkYWQgYWxndW5hIGVuIGNhc28gZGUgcXVlIHNlIHByb2R1emNhIHVuYSB2aW9sYWNpw7NuIGRlIGRlcmVjaG9zIGRlIHByb3BpZWRhZCBhbCBkaXN0cmlidWlyIGVzdG9zIGZpY2hlcm9zIG8gbWV0YWRhdG9zLgrigKIgVHJhYmFqb3MgZGVzcG9zaXRhZG9zIHBvciBvdHJvcyBxdWUgbm8gc2VhbiBzdSBhdXRvcjpkZWNsYXJvIHF1ZSBsb3MgbWV0YWRhdG9zIGJpYmxpb2dyw6FmaWNvcyBxdWUgZXN0b3kgYXJjaGl2YW5kbyBlbiBlbCByZXBvc3RvcmlvIGluc3RpdHVjaW9uYWwgZGUgbGEgVW5pdmVyc2lhZCBDb21wbHV0ZW5zZSBkZSBNYWRyaWQsIHNvbiBkZSBkb21pbmlvIHDDumJsaWNvLiBTaSBubyBmdWVzZSBlbCBjYXNvLCBhY2VwdG8gcGxlbmEgcmVzcG9uc2FiaWxpZGFkIHBvciBjdWFscXVpZXIgaW5mcmFjY2nDs24gZGUgZGVyZWNob3MgZGUgYXR1b3IgcXVlIGNvbmxsZXZlIGxhIGRpc3RyaWJ1Y2nDs24gZGUgZXN0b3MgZmljaGVyb3MgbyBtZXRhZGF0b3MuCuKAoiBQb3IgdGFudG8sIHRvZG9zIGxvcyBtZXRhZGF0b3MgcHVibGljYWRvcyBlbiBlbCByZXBvc2l0b3JpbyBpbnN0aXR1Y2lvbmFsIGRlIGxhIFVuaXZlcnNpZGFkIENvbXBsdXRlbnNlIGRlIE1hZHJpZCwgZXN0w6FuIGRpc3BvbmlibGVzIGNvbiBsYSBsaWNlbmNpYSBDcmVhdGl2ZSBDb21tb25zIENDMCAxLjAgVW5pdmVyc2FsIE9mcmVjaW1pZW50byBhbCBEb21pbmlvIFDDumJsaWNvIChDQzAgMS4wKS4gRXN0YSBsaWNlbmNpYSBwZXJtaXRlIGNvcGlhciwgbW9kaWZpY2FyLCBkaXN0cmlidWlyLCByZXV0aWxpemFyIHkgY29tcGFydGlyIHDDumJsaWNhIHkgbGlicmVtZW50ZSBsb3MgbWV0YWRhdG9zIChpbmNsdXllbmRvIHN1IHVzbyBjb21lcmNpYWwpLCBzaW4gdGVuZXIgcXVlIHBlZGlyIHBlcm1pc28uIFNpIHRlcmNlcmFzIHBhcnRlcyB1c2FuIGVzdG9zIG1ldGFkYXRvcywgZGViZW4gaGFjZXIgdW4gcmVjb25vY2ltaWVudG8geSB1bmEgYXRyaWJ1Y2Npw7NuIGEgbGFzIGZ1ZW50ZXMgZGUgbG9zIG1pc21vcy4gTGEgcmV1dGlsaXphY2nDs24gZGUgZXN0b3MgbWV0YWRhdG9zIHRhbWJpw6luIGVzIGxpYnJlLCB0YWwgeSBjb21vIGVzdGFibGVjZSBsYSBsaWNlbmNpYSBkZSB1c28gQ0MwLgo= URL https://docta.ucm.es/bitstreams/700087b6-21d8-4c48-9ec3-0306bf92def3/download File MD5 ac9c89cbfa521f36b6d3442ba1130fd8 5840681 application/pdf ijms-24-11837-v2.pdf