Click and Patterned Functionalization of Graphene by Diels–Alder Reaction

Abstract

Chemical functionalization is a promising approach to controllably manipulate the characteristics of graphene. Here, we designed cis-dienes, featuring two dihydronaphthalene backbones, to decorate a graphene surface via Diels-Alder (DA) click reaction. The installation of a diene moiety into a nonplanar molecular structure to form cis-conformation enables a rapid (∼5 min) DA reaction between graphene and diene groups. Patterned graphene of sub-micrometer resolution can be obtained by easily soaking poly(methyl methacrylate)-masked graphene in solution of hydroxyl-substituted cis-diene at room temperature. The functionalization degree can be further controlled by carrying out the reaction at higher temperature. The present result gives important insight into the effect of molecular conformation on the graphene functionalization process, and provides an effective and facile method for graphene functionalization.

Microcontact Printing Patterning of an HOPG Surface by an Inverse Electron Demand Diels–Alder Reaction

“…[29] The unmodified HOPG and Fc-O-Tz modified surfaces were furtherc haracterized by XPS.X PS can be used to confirmt he presence of elements introduced to the HOPG through the Diels-Alder and retro-Diels-Alder reactions. [6,7] After the IEDDA reaction of tetrazine with HOPG, its surfacec onductivity can be evaluated using scanning electrochemical microscopy (SECM). Representative spectra are shown in Figure 2.…”

“…[7][8][9][10] For example, Haddon and co-workerss howed that graphite/graphenec an serve as a diene by reacting with tetracyanoethylene (TCNE) at room temperature. [7][8][9][10] For example, Haddon and co-workerss howed that graphite/graphenec an serve as a diene by reacting with tetracyanoethylene (TCNE) at room temperature.…”

“…[7][8][9][10] For example, Haddon and co-workerss howed that graphite/graphenec an serve as a diene by reacting with tetracyanoethylene (TCNE) at room temperature. [7] The Braunschweig group showed that cyclopentadiene can covalently react with ag raphene surface under high pressure Diels-Alder conditions. [8] Wana nd coworkers demonstrated that graphene can react with asterically strained cis-diene leadingt os urface modifications.…”

Spatially Resolved Covalent Functionalization Patterns on Graphene

“…Herein, we combine two competing reactions on ag raphene substrate to create functionalization patterns on amicrometer scale via the Mitsunobu reaction. [19] This non-trivial task has been approached from several directions,u sing for instance photolithography, [20] dip-pen lithography [21][22][23] or various writing techniques. The proposed methodology thus provides ap athwayf or local introduction of arbitrary functional groups on graphene.…”

“…[7][8][9] Although several approaches for covalent grafting have been reported, [10][11][12][13][14][15] only recently has the advancement towards specific applications revealed the need for spatially resolved methods that would provide patterned surface functionalization on the 2D material, [16][17][18] aiming at sophisticated sensor arrays or device mass production. [19] This non-trivial task has been approached from several directions,u sing for instance photolithography, [20] dip-pen lithography [21][22][23] or various writing techniques. [24][25][26] Using covalent modification for spatially resolved functionalization typically relies on preventing contact of the reagents with graphene,t hus implying the use of ar esist mask [27] or controlled deposition [28,29] at the nanoscale,w hich either adds more steps (with concomitant contamination [30] ) or severely limits the processing speed, respectively.P hotochemical reactions represent au nique alternative to the abovementioned two approaches [31] because photochemistry responds to illumination patterns without the need for aresist or spatially confined reagent deposition.…”