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Magnetic and Electrochemical Properties of aTEMPO-SubstitutedDisulfideDiradical in Solution,inthe Crystal, and on aSurface

AuthorsLloveras, Vega ; Badetti, Elena ; Wurst, Klaus; Chechik, Victor; Veciana, Jaume ; Vidal Gancedo, José
EPR spectroscopy
Intramolecular spin-exchange interaction
Self-assembled monolayers
X-ray diffraction
Issue Date26-Jan-2016
CitationChemistry - a European Journal 22 (5): 1805–1815 (2016)
AbstractA study of the magnetic and electrochemical properties of a TEMPO-substituted disulfide diradical in three different environments was carried out: in solution, in the crystal, and as a self-assembled monolayer (SAM) on an Au(111) substrate, and the relationship between them was explored. In solution, this flexible diradical shows a strong spin-exchange interaction between the two nitroxide functions that depends on the temperature and solvent. Structural, dynamic, and thermodynamic information has been extracted from the EPR spectra of this dinitroxide. The magnetic interactions in the crystal include intra- and intermolecular contributions, which have been studied separately and shown to be antiferromagnetic in both cases. Finally, we demonstrate that both the magnetic and electrochemical properties are preserved upon chemisorption of the diradical on a gold surface. The resulting SAM displayed anisotropic magnetic properties, and angle-resolved EPR spectra of the monocrystal allowed a rough determination of the orientation of the molecules in the SAM.
Publisher version (URL)http://dx.doi.org/10.1002/chem.201503306
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