Issue 33, 2017

Direct covalent grafting of an organic radical core on gold and silver

Abstract

The functionalisation of surfaces with organic radicals, such as perchlorotriphenylmethyl (PTM) radicals or tris(2,4,6-trichloro-phenyl)methyl (TTM) radicals, is appealing for the development of molecular spintronic devices. Conventionally, organic radicals are chemisorbed to metal substrates by using long alkyl or aromatic spacers resulting in a weak spin–electron coupling between the radical and the substrate. To circumvent this problem, here we have employed a new design strategy for the fabrication of radical self-assembled monolayers (r-SAMs). This newly designed radical–anchor (R–A) molecule, a TTM based radical disulfide (1), can be easily synthesized and it was here characterized by electron spin resonance (ESR), cyclic voltammetry (CV) and superconducting quantum interference device magnetometry (SQUID). We have succeeded in fabricating TTM based r-SAMs by using thiolate bonds (Au–S and Ag–S) where the TTM cores are only one-atom distance from the metal surface for the first time. The resultant robust 1/Au and 1/Ag r-SAMs were well characterized, and the electrochemical and the magnetic properties were unambiguously confirmed, proving the persistence of the molecular spin.

Graphical abstract: Direct covalent grafting of an organic radical core on gold and silver

Supplementary files

Article information

Article type
Paper
Submitted
09 Feb 2017
Accepted
24 Mar 2017
First published
05 Apr 2017
This article is Open Access
Creative Commons BY license

RSC Adv., 2017,7, 20076-20083

Direct covalent grafting of an organic radical core on gold and silver

M. R. Ajayakumar, I. Alcón, S. T. Bromley, J. Veciana, C. Rovira and M. Mas-Torrent, RSC Adv., 2017, 7, 20076 DOI: 10.1039/C7RA01686G

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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