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The Challenge of Thermal Deposition of Coordination Compounds: Insight into the Case of an Fe4 Single Molecule Magnet

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Department of Chemistry “Ugo Schiff” and INSTM Research Unit, University of Florence, 50019 Sesto Fiorentino, Italy
Department of Chemical and Geological Sciences and INSTM Research Unit, University of Modena and Reggio Emilia, 41125 Modena, Italy
Cite this: Chem. Mater. 2016, 28, 21, 7693–7702
Publication Date (Web):September 26, 2016
Copyright © 2016 American Chemical Society

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Abstract Image

Realization of well-controlled hybrid interfaces between solid surfaces and functional complex molecules can be hampered by the presence of contaminants originated by the fragmentation of fragile architectures based on the coordinative bond. Here, we present a morphological and spectroscopic analysis of submonolayer films obtained by sublimation of the [Fe4(L)2(dpm)6] (Fe4) single molecule magnet on different substrates. Though intact tetranuclear molecules can be transferred to surfaces, smaller molecular species are often codeposited. By comparison of substrates characterized by different reactivities, such as Au(111), Cu(100), and Cu2N, and employing a protocol of indirect exposure of the substrate, we infer that the observed fragments do not originate from the reaction of Fe4 molecules with the surface but rather are produced during Fe4 sublimation, which releases Fe(dpm)3 as a very volatile compound. Fe(dpm)3 undergoes substrate-dependent on-surface decomposition to final products that have been identified by combined STM, UPS, XPS, and DFT studies.

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.chemmater.6b02696.

  • STM image analysis, including height distribution of Figure 1c, dimension analysis of the 2nd-layer Fe4 molecules of Figure 1d, height estimation of the B layer on Cu(100), lateral dimension analysis of Fe4 molecules on Cu(100), preliminary characterization of the Cu2N/Cu(100) surface, height estimation of B molecules on Cu2N, lateral dimension analysis of Fe4 molecules on Cu2N, comparison between the surface area covered by Fe4 and B molecules, setup for back-exposure experiments, ftf pairs of bi-lobed units on Au(111); XPS semiquantitative analysis; and DFT calculations (PDF)

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Cited By

This article is cited by 11 publications.

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  2. Luca Gragnaniello, Fabian Paschke, Philipp Erler, Peter Schmitt, Nicole Barth, Sabina Simon, Harald Brune, Stefano Rusponi, and Mikhail Fonin . Uniaxial 2D Superlattice of Fe4 Molecular Magnets on Graphene. Nano Letters 2017, 17 (12) , 7177-7182.
  3. Guillem Gabarró-Riera, Guillem Aromí, E. Carolina Sañudo. Magnetic molecules on surfaces: SMMs and beyond. Coordination Chemistry Reviews 2023, 475 , 214858.
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  9. Andrea Cornia, Matteo Mannini, Roberta Sessoli, Dante Gatteschi. Propeller‐Shaped Fe 4 and Fe 3 M Molecular Nanomagnets: A Journey from Crystals to Addressable Single Molecules. European Journal of Inorganic Chemistry 2019, 2019 (5) , 552-568.
  10. Irene Cimatti, Xiaohui Yi, Roberta Sessoli, Marin Puget, Boris Le Guennic, Julie Jung, Thierry Guizouarn, Agnese Magnani, Kevin Bernot, Matteo Mannini. Chemical tailoring of Single Molecule Magnet behavior in films of Dy(III) dimers. Applied Surface Science 2018, 432 , 7-14.
  11. Guglielmo Fernandez Garcia, Alessandro Lunghi, Federico Totti, Roberta Sessoli. The disclosure of mesoscale behaviour of a 3d-SMM monolayer on Au(111) through a multilevel approach. Nanoscale 2018, 10 (8) , 4096-4104.

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