Covalent Modification of Highly Ordered Pyrolytic Graphite with a Stable Organic Free Radical by Using Diazonium Chemistry

Gonca Seber; Alexander V. Rudnev; Andrea Droghetti; Ivan Rungger; Jaume Veciana; Marta Mas-Torrent; Concepció Rovira; Núria Crivillers

doi:10.1002/chem.201604700

Covalent Modification of Highly Ordered Pyrolytic Graphite with a Stable Organic Free Radical by Using Diazonium Chemistry

Gonca Seber, Alexander V. Rudnev, Andrea Droghetti, Ivan Rungger, Jaume Veciana, Marta Mas-Torrent, Concepció Rovira, Núria Crivillers

Research output: Contribution to journal › Article › Research › peer-review

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Abstract

© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim A 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.

Original language	English
Pages (from-to)	1415-1421
Journal	Chemistry - A European Journal
Volume	23
Issue number	6
DOIs	https://doi.org/10.1002/chem.201604700
Publication status	Published - 1 Jan 2017

Keywords

diazonium compounds
electrochemistry
radicals
redox chemistry
surface chemistry

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10.1002/chem.201604700

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title = "Covalent Modification of Highly Ordered Pyrolytic Graphite with a Stable Organic Free Radical by Using Diazonium Chemistry",

abstract = "{\textcopyright} 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim A 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.",

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author = "Gonca Seber and Rudnev, {Alexander V.} and Andrea Droghetti and Ivan Rungger and Jaume Veciana and Marta Mas-Torrent and Concepci{\'o} Rovira and N{\'u}ria Crivillers",

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doi = "10.1002/chem.201604700",

language = "English",

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T1 - Covalent Modification of Highly Ordered Pyrolytic Graphite with a Stable Organic Free Radical by Using Diazonium Chemistry

AU - Seber, Gonca

AU - Rudnev, Alexander V.

AU - Droghetti, Andrea

AU - Rungger, Ivan

AU - Veciana, Jaume

AU - Mas-Torrent, Marta

AU - Rovira, Concepció

AU - Crivillers, Núria

PY - 2017/1/1

Y1 - 2017/1/1

N2 - © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim A 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.

AB - © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim A 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.

KW - diazonium compounds

KW - electrochemistry

KW - radicals

KW - redox chemistry

KW - surface chemistry

U2 - 10.1002/chem.201604700

DO - 10.1002/chem.201604700

M3 - Article

VL - 23

SP - 1415

EP - 1421

IS - 6

ER -

Covalent Modification of Highly Ordered Pyrolytic Graphite with a Stable Organic Free Radical by Using Diazonium Chemistry

Abstract

Keywords

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