title: Diels-Alder Reaction of Anthranilic Acids: A Versatile Route to Dense Monolayers on Flat Edge and Basal Plane Graphitic Carbon Substrates.
abstract: Methods that reliably yield monolayers of covalently anchored modifiers on graphene and other planar graphitic materials are in demand. Covalently bonded groups can add functionality to graphitic carbon for applications ranging from sensing to supercapacitors and can tune the electronic and optical properties of graphene. Limiting modification to a monolayer gives a layer with well-defined concentration and thickness providing a minimum barrier to charge transfer. Here we investigate the use of anthranilic acid derivatives for grafting aryl groups to few layer graphene and pyrolyzed photoresist film (PPF). Under mild conditions, anthranilic acids generate arynes, which undergo Diels-Alder cycloadditions. Using spectroscopy, electrochemistry, and atomic force microscopy, we demonstrate that the reaction yields monolayers of aryl groups on graphene and PPF with maximum surface coverages consistent with densely packed layers. Our study confirms that anthranilic acids offer a convenient route to covalent modification of planar graphitic carbons (both basal and edge plane materials).
authors.affiliation: MacDiarmid Institute for Advanced Materials and Nanotechnology, Department of Chemistry, University of Canterbury , Private Bag 4800, Christchurch 8140, New Zealand.
authors.forename: Anna K
authors.initials: AK
authors.lastname: Farquhar
authors.affiliation: Department of Chemistry, University of Canterbury , Private Bag 4800, Christchurch 8140, New Zealand.
authors.forename: Christopher M
authors.initials: CM
authors.lastname: Fitchett
authors.affiliation: MacDiarmid Institute for Advanced Materials and Nanotechnology, Chemistry-Institute of Fundamental Sciences, Massey University , Private Bag 11 222, Palmerston North 4442, New Zealand.
authors.forename: Haidee M
authors.initials: HM
authors.lastname: Dykstra
authors.affiliation: MacDiarmid Institute for Advanced Materials and Nanotechnology, Chemistry-Institute of Fundamental Sciences, Massey University , Private Bag 11 222, Palmerston North 4442, New Zealand.
authors.forename: Mark R
authors.initials: MR
authors.lastname: Waterland
authors.affiliation: MacDiarmid Institute for Advanced Materials and Nanotechnology, Department of Chemistry, University of Canterbury , Private Bag 4800, Christchurch 8140, New Zealand.
authors.forename: Paula A
authors.initials: PA
authors.lastname: Brooksby
authors.affiliation: MacDiarmid Institute for Advanced Materials and Nanotechnology, Department of Chemistry, University of Canterbury , Private Bag 4800, Christchurch 8140, New Zealand.
authors.forename: Alison J
authors.initials: AJ
authors.lastname: Downard
keywords: PPF; aryne; cycloaddition; glassy carbon; grafting; graphene; pyrolyzed photoresist film