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Keywords = transition metal porphyrinato complexes

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16 pages, 3093 KiB  
Article
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
by Silvia Carlotto, Iulia Cojocariu, Vitaliy Feyer, Luca Floreano and Maurizio Casarin
Nanomaterials 2022, 12(2), 218; https://doi.org/10.3390/nano12020218 - 10 Jan 2022
Cited by 8 | Viewed by 2484
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 [...] Read more.
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. Full article
(This article belongs to the Special Issue Density Functional Theory Simulations of Nanostructures)
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