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Magnetic and Electrochemical Properties of a TEMPO‐Substituted Disulfide Diradical in Solution, in the Crystal, and on a Surface
Author(s) -
Lloveras Vega,
Badetti Elena,
Wurst Klaus,
Chechik Victor,
Veciana Jaume,
VidalGancedo José
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201503306
Subject(s) - diradical , disulfide bond , electrochemistry , crystal (programming language) , surface (topology) , chemistry , materials science , crystallography , computer science , mathematics , electrode , physics , atomic physics , biochemistry , geometry , singlet state , programming language , excited state
Abstract A 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.