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

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

Shekhah, O. / Veciana, J. / Ocal, C. / Roques, N. / Mugnaini, V. / Munuera, C. / Wöll, Ch. (2008)

place:

Langmuir 24 (2008), 13, 6640-6648

Date: 2008

Shekhah, O. / Veciana, J. / Ocal, C. / Roques, N. / Mugnaini, V. / Munuera, C. / Wöll, Ch. (2008): "Grafting of monocarboxylic substituted polychlorotriphenylmethyl radicals onto a COOH-functionalized self-assembled monolayer through copper (II) metal ions". In: Langmuir 24 (2008), 13, 6640-6648

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 mu CP 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.


 

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