Driving forces for covalent assembly of porphyrins by selective C-H bond activation and intermolecular coupling on a copper surface

Floris, Andrea and Haq, Sam and In’t Veld, Mendel and Amabilino, David and Raval, Rasmita and Kantorovich, Lev (2016) Driving forces for covalent assembly of porphyrins by selective C-H bond activation and intermolecular coupling on a copper surface. Journal of the American Chemical Society, 138 (18). pp. 5837-5847. ISSN 0002-7863

Full content URL: http://doi.org/10.1021/jacs.5b11594

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Abstract

Recent synthesis of covalent organic assemblies at surfaces has opened up the promise of producing robust nanostructures for functional interfaces. To uncover how this new chemistry works at surfaces and understand the underlying mechanism(s) that control bond-breaking and bond-making processes at specific positions of the participating molecules, we study here the coupling reaction of tetra(mesityl)porphyrin molecules, which creates covalently connected networks on the Cu(110) surface by utilising the 4-methyl groups as unique connection points. Using scanning tunneling microscopy (STM), state-of-the-art density functional theory (DFT) and Nudged Elastic Band (NEB) calculations, we show that the unique directionality of the covalent bonding is found to stem from a chain of highly selective C-H activation and dehydrogenation processes, followed by specific intermolecular C-C coupling reactions that are facilitated by the surface, by steric constraints and by anisotropic molecular diffusion. These insights provide the first steps towards developing synthetic rules for complex two-dimensional covalent organic chemistry that can be enacted directly at a surface to deliver specific macromolecular structures designed for specific functions.

Keywords:covalent assembly, on-surface synthesis, porphyrins, density functional theory (DFT), scanning tunneling microscopy (STM), molecular diffusion, NotOAChecked
Subjects:F Physical Sciences > F200 Materials Science
F Physical Sciences > F300 Physics
F Physical Sciences > F343 Computational Physics
Divisions:College of Science > School of Mathematics and Physics
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ID Code:23233
Deposited On:02 Jun 2016 19:39

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