Luminescence and Excited-State Reactivity in a Heteroleptic Tricyanido Fe(III) Complex Ye, Yating Garrido Barros, Pablo Wellauer, Joël Moreno Cruz, Carlos Lescouëzec, Rodrigue Wenger, Oliver S. Herrera Martínez, Juan Manuel Jiménez Gallego, Juan Ramón Harnessing sunlight via photosensitizing molecules is key for novel optical applications and solar-to-chemical energy conversion. Exploiting abundant metals such as iron is attractive but becomes challenging due to typically fast nonradiative relaxation processes. In this work, we report on the luminescence and excited-state reactivity of the heteroleptic [FeIII(pzTp)- (CN)3]− complex (pzTp = tetrakis(pyrazolyl)borate), which incorporates a σ-donating trispyrazolyl chelate ligand and three monodentate σ-donating and π-accepting cyanide ligands. Contrary to the nonemissive [Fe(CN)6]3−, a broad emission band centered at 600 nm at room temperature has been recorded for the heteroleptic analogue attributed to the radiative deactivation from a 2LMCT excited state with a luminescence quantum yield of 0.02% and a lifetime of 80 ps in chloroform at room temperature. Bimolecular reactivity of the 2LMCT excited state was successfully applied to different alcohol photo-oxidation, identifying a cyanide−H bonding as a key reaction intermediate. Finally, this research demonstrated the exciting potential of [Fe(pzTp)(CN)3]− as a photo-oxidant, paving the way for further exploration and development of emissive Fe-based photosensitizers competent for photochemical transformations. 2024-05-13T06:53:37Z 2024-05-13T06:53:37Z 2023-12-29 journal article Yating Ye, Pablo Garrido-Barros, Joël Wellauer, Carlos M. Cruz, Rodrigue Lescouëzec, Oliver S. Wenger, Juan Manuel Herrera, and Juan-Ramón Jiménez Journal of the American Chemical Society 2024 146 (1), 954-960 DOI: 10.1021/jacs.3c11517 https://hdl.handle.net/10481/91685 10.1021/jacs.3c11517 eng info:eu-repo/grantAgreement/EC/NextGenerationEU/TED2021.129598A.I00 info:eu-repo/grantAgreement/EC/NextGenerationEU/IJC2020-044040-I info:eu-repo/grantAgreement/EC/NextGenerationEU/RYC2021-031249-I http://creativecommons.org/licenses/by/4.0/ open access Atribución 4.0 Internacional American Chemical Society