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Covalent Modification of Highly Ordered Pyrolytic Graphite withaStable OrganicFree Radical by UsingDiazonium Chemistry

AutorSeber, Gonca; Rudnev, Alexander V.; Droghetti, Andrea; Rungger, Ivan; Veciana Miró, Jaume; Mas-Torrent, Marta; Rovira Angulo, Concepció; Crivillers Clusella, Nuria
Palabras claveDiazonium compounds
Redox chemistry
Surface chemistry
Fecha de publicación26-ene-2017
CitaciónChemistry - a European Journal 23(6): 1415–1421 (2017)
ResumenA novel, persistent, electrochemically active perchlorinated triphenylmethyl (PTM) radical with a diazonium functionality has been covalently attached to highly ordered pyrolytic graphite (HOPG) by electrografting in a single-step process. Electrochemical scanning tunneling microscopy (EC-STM) and Raman spectroscopy measurements revealed that PTM molecules had a higher tendency to covalently react at the HOPG step edges. The cross-section profiles from EC-STM images showed that there was current enhancement at the functionalized areas, which could be explained by redox-mediated electron tunneling through surface-confined redox-active molecules. Cyclic voltammetry clearly demonstrated that the intrinsic properties of the organic radical were preserved upon grafting and DFT calculations also revealed that the magnetic character of the PTM radical was preserved.
Versión del editorhttp://dx.doi.org/10.1002/chem.201604700
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