Unveiling the formation mechanism of the biphenylene network

Abstract

We have computationally studied the formation mechanism of the biphenylene network via the intermolecular HF zipping, as well as identified key intermediates experimentally, on the Au(111) surface. We elucidate that the zipping process consists of a series of defluorinations, dehydrogenations, and C–C coupling reactions. The Au substrate not only serves as the active site for defluorination and dehydrogenation, but also forms C–Au bonds that stabilize the defluorinated and dehydrogenated phenylene radicals, leading to “standing” benzyne groups. Despite that the C–C coupling between the “standing” benzyne groups is identified as the rate-limiting step, the limiting barrier can be reduced by the adjacent chemisorbed benzyne groups. The theoretically proposed mechanism is further supported by scanning tunneling microscopy experiments, in which the key intermediate state containing chemisorbed benzyne groups can be observed. This study provides a comprehensive understanding towards the on-surface intermolecular HF zipping, anticipated to be instructive for its future applications.

Graphical abstract: Unveiling the formation mechanism of the biphenylene network

Supplementary files

Article information

Article type
Communication
Submitted
07 Nov 2022
Accepted
03 Jan 2023
First published
03 Jan 2023
This article is Open Access
Creative Commons BY license

Nanoscale Horiz., 2023, Advance Article

Unveiling the formation mechanism of the biphenylene network

K. Niu, Q. Fan, L. Chi, J. Rosen, J. M. Gottfried and J. Björk, Nanoscale Horiz., 2023, Advance Article , DOI: 10.1039/D2NH00528J

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