Covalent C–N Bond Formation Through a Surface Catalyzed Thermal Cyclodehydrogenation

Journal Of The American Chemical Society 142,8, 3696 - 3700 (2020)

Covalent C–N Bond Formation Through a Surface Catalyzed Thermal Cyclodehydrogenation

Ilya Piskun,Raymond Blackwell,Joaquim Jornet-Somoza,Fangzhou Zhao, Angel Rubio,Steven G. Louie, Felix R. Fischer

The integration of substitutional dopants at predetermined positions along the hexagonal lattice of graphene- derived polycyclic aromatic hydrocarbons is a critical tool in the design of functional electronic materials. Here we report the unusually mild thermally induced oxidative cyclodehydrogenation of dianthryl pyrazino[2,3-g]quinoxalines to form the four covalent C–N bond in tetraazateranthene on Au(111) and Ag(111) surfaces. Bondresolved scanning probe microscopy, differential conductance spectroscopy, along with first principles calculations unambiguously confirm the structural assignment. Detailed mechanistic analysis based on ab -initio DFT calculations reveals a stepwise mechanism featuring a rate determining barrier of only DE‡ = 0.6 eV, consistent with the experimentally observed reaction conditions.

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Research supported by the Office of Naval Research MURI Program N00014-16-1-2921 (design and synthesis of molecular precursors and theoretical analyses), the Center for Energy Efficient Electronics NSF Award 0939514 (SPM and STS), and the National Science Foundation under grant DMR-1926004 (DFT and GW calculations). AR was supported by the European Research Council (ERC-2015-AdG694097) and Grupos Consolidados (IT1249-19). Berkeley NMR Facility is supported in part by NIH grants 1S10RR016634-01,SRR023679A, and S10OD024998. JJS acknowledges funding from the European Union Horizon 2020 research and innovation program under the Marie Sklodowska-Curie Grant Agreement No. 795246-StrongLights.

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