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

Research output: Contribution to journalArticle

Andrea Floris, Sam Haq, Mendel In’t Veld, David B. Amabilino, Rasmita Raval, Lev Kantorovitch

Original languageEnglish
Pages (from-to)5837-5847
Number of pages11
JournalJournal of The American Chemistry Society
Volume138
Issue number18
Early online date20 Apr 2016
DOIs
Accepted/In press20 Apr 2016
E-pub ahead of print20 Apr 2016
Published11 May 2016

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Abstract

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 func-
tional 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.

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