@misc{10481/91685,
year = {2023},
month = {12},
url = {https://hdl.handle.net/10481/91685},
abstract = {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.},
organization = {Grant TED2021.129598A.I00 funded by MCIN/AEI/10.13039/501100011033 and by European Union NextGenerationEU/PRTR and Junta de Andalucía},
organization = {Juan de la Cierva Incorporation grant IJC2020-044040-I funded by MCIN/AEI/10.13039/501100011033 and by European Union NextGenerationEU/PRTR},
organization = {Ramón y Cajal grant RYC2021-031249-I funded by MCIN/AEI/10.13039/501100011033 and by European Union NextGenerationEU/PRTR},
organization = {Ministerio de Ciencia e Innovación (PGC2018 102052-B-C21) MCIN/AEI/10.13039/501100011033/ FEDER “Una manera de hacer Europa”},
organization = {Junta de Andalucía
(FQM-195, projects I + D + i A-FQM-172-UGR18 and
B.FQM.328.UGR20)},
organization = {University of Granada},
organization = {Junta de Andalucía for a postdoctoral grant
(POSTDOC_21_00139)},
organization = {Funding for open access charge: Universidad de Granada /
CBUA.},
publisher = {American Chemical Society},
title = {Luminescence and Excited-State Reactivity in a Heteroleptic Tricyanido Fe(III) Complex},
doi = {10.1021/jacs.3c11517},
author = {Ye, Yating and Garrido Barros, Pablo and Wellauer, Joël and Moreno Cruz, Carlos and Lescouëzec, Rodrigue and Wenger, Oliver S. and Herrera Martínez, Juan Manuel and Jiménez Gallego, Juan Ramón},
}