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Ferrous to Ferric Transition in Fe‐Phthalocyanine Driven by NO(2) Exposure

Due to its unique magnetic properties offered by the open‐shell electronic structure of the central metal ion, and for being an effective catalyst in a wide variety of reactions, iron phthalocyanine has drawn significant interest from the scientific community. Nevertheless, upon surface deposition,...

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Autores principales: Cojocariu, Iulia, Carlotto, Silvia, Sturmeit, Henning Maximilian, Zamborlini, Giovanni, Cinchetti, Mirko, Cossaro, Albano, Verdini, Alberto, Floreano, Luca, Jugovac, Matteo, Puschnig, Peter, Piamonteze, Cinthia, Casarin, Maurizio, Feyer, Vitaliy, Schneider, Claus Michael
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2021
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7898877/
https://www.ncbi.nlm.nih.gov/pubmed/33264485
http://dx.doi.org/10.1002/chem.202004932
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author Cojocariu, Iulia
Carlotto, Silvia
Sturmeit, Henning Maximilian
Zamborlini, Giovanni
Cinchetti, Mirko
Cossaro, Albano
Verdini, Alberto
Floreano, Luca
Jugovac, Matteo
Puschnig, Peter
Piamonteze, Cinthia
Casarin, Maurizio
Feyer, Vitaliy
Schneider, Claus Michael
author_facet Cojocariu, Iulia
Carlotto, Silvia
Sturmeit, Henning Maximilian
Zamborlini, Giovanni
Cinchetti, Mirko
Cossaro, Albano
Verdini, Alberto
Floreano, Luca
Jugovac, Matteo
Puschnig, Peter
Piamonteze, Cinthia
Casarin, Maurizio
Feyer, Vitaliy
Schneider, Claus Michael
author_sort Cojocariu, Iulia
collection PubMed
description Due to its unique magnetic properties offered by the open‐shell electronic structure of the central metal ion, and for being an effective catalyst in a wide variety of reactions, iron phthalocyanine has drawn significant interest from the scientific community. Nevertheless, upon surface deposition, the magnetic properties of the molecular layer can be significantly affected by the coupling occurring at the interface, and the more reactive the surface, the stronger is the impact on the spin state. Here, we show that on Cu(100), indeed, the strong hybridization between the Fe d‐states of FePc and the sp‐band of the copper substrate modifies the charge distribution in the molecule, significantly influencing the magnetic properties of the iron ion. The Fe(II) ion is stabilized in the low singlet spin state (S=0), leading to the complete quenching of the molecule magnetic moment. By exploiting the FePc/Cu(100) interface, we demonstrate that NO(2) dissociation can be used to gradually change the magnetic properties of the iron ion, by trimming the gas dosage. For lower doses, the FePc film is decoupled from the copper substrate, restoring the gas phase triplet spin state (S=1). A higher dose induces the transition from ferrous to ferric phthalocyanine, in its intermediate spin state, with enhanced magnetic moment due to the interaction with the atomic ligands. Remarkably, in this way, three different spin configurations have been observed within the same metalorganic/metal interface by exposing it to different doses of NO(2) at room temperature.
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spelling pubmed-78988772021-03-03 Ferrous to Ferric Transition in Fe‐Phthalocyanine Driven by NO(2) Exposure Cojocariu, Iulia Carlotto, Silvia Sturmeit, Henning Maximilian Zamborlini, Giovanni Cinchetti, Mirko Cossaro, Albano Verdini, Alberto Floreano, Luca Jugovac, Matteo Puschnig, Peter Piamonteze, Cinthia Casarin, Maurizio Feyer, Vitaliy Schneider, Claus Michael Chemistry Full Papers Due to its unique magnetic properties offered by the open‐shell electronic structure of the central metal ion, and for being an effective catalyst in a wide variety of reactions, iron phthalocyanine has drawn significant interest from the scientific community. Nevertheless, upon surface deposition, the magnetic properties of the molecular layer can be significantly affected by the coupling occurring at the interface, and the more reactive the surface, the stronger is the impact on the spin state. Here, we show that on Cu(100), indeed, the strong hybridization between the Fe d‐states of FePc and the sp‐band of the copper substrate modifies the charge distribution in the molecule, significantly influencing the magnetic properties of the iron ion. The Fe(II) ion is stabilized in the low singlet spin state (S=0), leading to the complete quenching of the molecule magnetic moment. By exploiting the FePc/Cu(100) interface, we demonstrate that NO(2) dissociation can be used to gradually change the magnetic properties of the iron ion, by trimming the gas dosage. For lower doses, the FePc film is decoupled from the copper substrate, restoring the gas phase triplet spin state (S=1). A higher dose induces the transition from ferrous to ferric phthalocyanine, in its intermediate spin state, with enhanced magnetic moment due to the interaction with the atomic ligands. Remarkably, in this way, three different spin configurations have been observed within the same metalorganic/metal interface by exposing it to different doses of NO(2) at room temperature. John Wiley and Sons Inc. 2021-01-25 2021-02-15 /pmc/articles/PMC7898877/ /pubmed/33264485 http://dx.doi.org/10.1002/chem.202004932 Text en © 2020 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH This is an open access article under the terms of the http://creativecommons.org/licenses/by/4.0/ License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
spellingShingle Full Papers
Cojocariu, Iulia
Carlotto, Silvia
Sturmeit, Henning Maximilian
Zamborlini, Giovanni
Cinchetti, Mirko
Cossaro, Albano
Verdini, Alberto
Floreano, Luca
Jugovac, Matteo
Puschnig, Peter
Piamonteze, Cinthia
Casarin, Maurizio
Feyer, Vitaliy
Schneider, Claus Michael
Ferrous to Ferric Transition in Fe‐Phthalocyanine Driven by NO(2) Exposure
title Ferrous to Ferric Transition in Fe‐Phthalocyanine Driven by NO(2) Exposure
title_full Ferrous to Ferric Transition in Fe‐Phthalocyanine Driven by NO(2) Exposure
title_fullStr Ferrous to Ferric Transition in Fe‐Phthalocyanine Driven by NO(2) Exposure
title_full_unstemmed Ferrous to Ferric Transition in Fe‐Phthalocyanine Driven by NO(2) Exposure
title_short Ferrous to Ferric Transition in Fe‐Phthalocyanine Driven by NO(2) Exposure
title_sort ferrous to ferric transition in fe‐phthalocyanine driven by no(2) exposure
topic Full Papers
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7898877/
https://www.ncbi.nlm.nih.gov/pubmed/33264485
http://dx.doi.org/10.1002/chem.202004932
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