Grafting of monocarboxylic substituted polychlorotriphenylmethyl radicals onto a COOH-functionalized self-assembled monolayer through copper (II) metal ions

Osama Shekhah, N. Roques, V. Mugnaini, C. Munuera, C. Ocal, J. Veciana*, C. Wöll

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

46 Scopus citations

Abstract

A monocarboxylic substituted polychlorotriphenylmethyl radical (PTMCOOH) has been grafted onto a COOH-functionalized SAM (mercaptohexadecanoic acid, MHDA SAM), using copper (II) metal ions as linkers between the carboxyl groups of the SAM and the ligand. The metal-radical adlayer has been characterized thoroughly using different surface analysis techniques, such as contact angle, IRRAS, XPS, SPR, ToF-SIMS, SFM, and NEXAFS. The magnetic character was confirmed by EPR. The density of unoccupied states was investigated using X-ray absorption spectroscopy. A low-energy peak in the NEXAFS spectrum directly revealed the presence of partially occupied electronic levels, thus proving the open-shell character of the grafted ligands. SEM measurements on a laterally patterned sample prepared by μCP of MHDA in a matrix of hexadecane thiolate (a CH3-terminated SAM) was performed to demonstrate that the metal-assisted anchoring of the open-shell ligand occurs selectively on the COOH terminated SAM. These results represent an easy and new approach to anchor organic radicals on surfaces and constitute a first step toward the growth of magnetic metal-organic radical-based frameworks on solid substrates.

Original languageEnglish (US)
Pages (from-to)6640-6648
Number of pages9
JournalLangmuir
Volume24
Issue number13
DOIs
StatePublished - Jul 1 2008

ASJC Scopus subject areas

  • Materials Science(all)
  • Condensed Matter Physics
  • Surfaces and Interfaces
  • Spectroscopy
  • Electrochemistry

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