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Driving Forces for Covalent Assembly of Porphyrins by Selective C-H Bond Activation and Intermolecular Coupling on a Copper Surface

Floris, Andrea; Haq, Sam; Veld, Mendel In't; Amabilino, David A.; Raval, Rasmita; Kantorovich, Lev

Driving Forces for Covalent Assembly of Porphyrins by Selective C-H Bond Activation and Intermolecular Coupling on a Copper Surface Thumbnail


Authors

Andrea Floris

Sam Haq

Mendel In't Veld

David A. Amabilino

Rasmita Raval

Lev Kantorovich



Abstract

© 2016 American Chemical Society. Recent synthesis of covalent organic assemblies at surfaces has opened the promise of producing robust nanostructures for functional interfaces. To uncover how this new chemistry works at surfaces and understand the underlying mechanisms 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 utilizing 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 toward 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.

Citation

Floris, A., Haq, S., Veld, M. I., Amabilino, D. A., Raval, R., & Kantorovich, L. (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), 5837-5847. https://doi.org/10.1021/jacs.5b11594

Journal Article Type Article
Acceptance Date Apr 19, 2016
Online Publication Date May 2, 2016
Publication Date May 11, 2016
Deposit Date Aug 25, 2016
Publicly Available Date Mar 29, 2024
Journal Journal of the American Chemical Society
Print ISSN 0002-7863
Electronic ISSN 1520-5126
Publisher American Chemical Society
Peer Reviewed Peer Reviewed
Volume 138
Issue 18
Pages 5837-5847
DOI https://doi.org/10.1021/jacs.5b11594
Public URL https://nottingham-repository.worktribe.com/output/790442
Publisher URL http://pubs.acs.org/doi/abs/10.1021/jacs.5b11594
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.

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