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 Veld, Mendel In't and Amabilino, David A. 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 1520-5126

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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 de-hydrogenation 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.

Item Type: Article
Additional Information: This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of the American Chemical Society, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/doi/abs/10.1021/jacs.5b11594.
Schools/Departments: University of Nottingham UK Campus > Faculty of Science > School of Chemistry
Identification Number: https://doi.org/10.1021/jacs.5b11594
Depositing User: Bramwell, Roseanna
Date Deposited: 25 Aug 2016 10:33
Last Modified: 19 Sep 2016 00:17
URI: http://eprints.nottingham.ac.uk/id/eprint/36028

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