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Photocatalytic Aerobic Dehydrogenation of N-Heterocycles with Ir(III) Photosensitizers Bearing the 2(2′-Pyridyl)benzimidazole Scaffold Echevarría Poza, Igor Vaquero Gutiérrez, Mónica Manzano, Blanca R. Jalón Sotés, Félix Ángel Quesada Pato, Roberto Espino Ordóñez, Gustavo Excited states Ligands Redox reactions Solvents Transition metals Química inorgánica Química orgánica Chemistry, Inorganic Chemistry, Organic Photoredox catalysis constitutes a very powerful tool in organic synthesis, due to its versatility, efficiency, and the mild conditions required by photoinduced transformations. In this paper, we present an efficient and selective photocatalytic procedure for the aerobic oxidative dehydrogenation of partially saturated N-heterocycles to afford the respective N-heteroarenes (indoles, quinolines, acridines, and quinoxalines). The protocol involves the use of new Ir(III) biscyclometalated photocatalysts of the general formula [Ir(C^N)2(N^N′)]Cl, where the C^N ligand is 2- (2,4-difluorophenyl)pyridinate, and N^N′ are different ligands based on the 2-(2′-pyridyl)benzimidazole scaffold. In-depth electrochemical and photophysical studies as well as DFT calculations have allowed us to establish structure−activity relationships, which provide insights for the rational design of efficient metal-based dyes in photocatalytic oxidation reactions. In addition, we have formulated a dual mechanism, mediated by the radical anion superoxide, for the above-mentioned transformations. We acknowledge the financial support provided by the Spanish Ministerio de Ciencia, Innovación y Universidades (RTI2018- 100709-B-C21 and CTQ (QMC)-RED2018-102471-T), Consejería de Educación de la Junta de Castilla y León and FEDER (BU087G19 and BU067P20), and Junta de Comunidades de Castilla-La Mancha-FEDER (JCCM) (grant SBPLY/19/ 180501/000260). I.E. acknowledges his fellowship to both the European Social Fund and Consejería de Educación de la Junta de Castilla y León (EDU/1100/2017). We are also indebted to J. Delgado, P. Castroviejo, and M. Mansilla (PCT of the Universidad de Burgos) for technical support, G. GarcíaHerbosa for providing us access to CV equipment, and J. V. Cuevas-Vicario for support with Gaussian. 2023-02-07T09:18:18Z 2023-02-07T09:18:18Z 2022-04 info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion 0020-1669 http://hdl.handle.net/10259/7407 10.1021/acs.inorgchem.2c00358 1520-510X eng Inorganic Chemistry. 2022, V. 61, n. 16, p. 6193-6208 https://doi.org/10.1021/acs.inorgchem.2c00358 info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/RTI2018-100709-B-C21/ES/NUEVOS METALOFARMACOS DISEÑADOS PARA INCREMENTAR LA SELECTIVIDAD EN TRATAMIENTOS CONTRA EL CANCER. USO DE FOTOTERAPIA Y VEHICULIZACION CON LIGANDOS DIRIGIDOS A TUMORES/ info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/RED2018-102471-T/ES/METALOFARMACOS MULTIFUNCIONALES PARA DIAGNOSIS Y TERAPIA/ info:eu-repo/grantAgreement/Junta de Castilla y León//BU087G19//Compuestos organometálicos de ir(iii) en terapias antiproliferativas y como sondas químicas deaminas biógenas/ info:eu-repo/grantAgreement/Junta de Castilla y León//BU067P20//Molecular tools targeting cellular metabolism for cancer therapy/ info:eu-repo/grantAgreement/JCCM//SBPLY%2F19%2F 180501%2F000260/ Atribución 4.0 Internacional http://creativecommons.org/licenses/by/4.0/ info:eu-repo/semantics/openAccess application/pdf American Chemical Society https://riubu.ubu.es/bitstream/10259/7407/4/Echevarria-ic_2022.pdf.jpg Hispana TEXT http://creativecommons.org/licenses/by/4.0/ RIUBU. Repositorio Institucional de la Universidad de Burgos http://hdl.handle.net/10259/7407