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The Magnetic Behaviour of CoTPP Supported on Coinage Metal Surfaces in the Presence of Small Molecules: A Molecular Cluster Study of the Surface trans-Effect

Authors :
Silvia Carlotto
Iulia Cojocariu
Vitaliy Feyer
Luca Floreano
Maurizio Casarin
Source :
Nanomaterials, Vol 12, Iss 2, p 218 (2022)
Publication Year :
2022
Publisher :
MDPI AG, 2022.

Abstract

Density functional theory, combined with the molecular cluster model, has been used to investigate the surface trans-effect induced by the coordination of small molecules L (L = CO, NH3, NO, NO2 and O2) on the cobalt electronic structure of cobalt tetraphenylporphyrinato (CoTPP) surface-supported on coinage metal surfaces (Cu, Ag, and Au). Regardless of whether L has a closed- or an open-shell electronic structure, its coordination to Co takes out the direct interaction between Co and the substrate eventually present. The CO and NH3 bonding to CoTPP does not influence the Co local electronic structure, while the NO (NO2 and O2) coordination induces a Co reduction (oxidation), generating a 3d8 CoI (3d6 CoIII) magnetically silent closed-shell species. Theoretical outcomes herein reported demonstrate that simple and computationally inexpensive models can be used not only to rationalize but also to predict the effects of the Co–L bonding on the magnetic behaviour of CoTPP chemisorbed on coinage metals. The same model may be straightforwardly extended to other transition metals or coordinated molecules.

Details

Language :
English
ISSN :
20794991
Volume :
12
Issue :
2
Database :
Directory of Open Access Journals
Journal :
Nanomaterials
Publication Type :
Academic Journal
Accession number :
edsdoj.48573c2d02c048028dcf0e19b4b2dc86
Document Type :
article
Full Text :
https://doi.org/10.3390/nano12020218