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Sterically selective [3+3] cycloaromatization in the on-surface synthesis of nanographenes

Amogh Kinikar1*, Xiao-Ye Wang2, Marco Di Giovannantonio1, José I. Urgel1, Pengcai Liu3, Kristjan Eimre1, Carlo Antonio Pignedoli1, Samuel Stolz1, Max Bommert1, Shantanu Mishra1, Qiang Sun1, Roland Widmer1, Zijie Qiu2, Akimitsu Narita1, Klaus Müllen2, Pascal Ruffieux1, Roman Fasel1

1 Empa, Swiss Federal Laboratories for Materials Science and Technology, 8600 Dübendorf (Switzerland)

2 Max Planck Institute for Polymer Research, 55128 Mainz (Germany)

3 State Key Laboratory of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin 300071 (China)

* Corresponding authors emails: amogh.kinikar@empa.ch
DOI10.24435/materialscloud:21-aj [version v1]

Publication date: Dec 20, 2023

How to cite this record

Amogh Kinikar, Xiao-Ye Wang, Marco Di Giovannantonio, José I. Urgel, Pengcai Liu, Kristjan Eimre, Carlo Antonio Pignedoli, Samuel Stolz, Max Bommert, Shantanu Mishra, Qiang Sun, Roland Widmer, Zijie Qiu, Akimitsu Narita, Klaus Müllen, Pascal Ruffieux, Roman Fasel, Sterically selective [3+3] cycloaromatization in the on-surface synthesis of nanographenes, Materials Cloud Archive 2023.198 (2023), https://doi.org/10.24435/materialscloud:21-aj


Surface-catalyzed reactions have been used to synthesize carbon nanomaterials with atomically pre-defined structures. The recent discovery of a gold surface-catalyzed [3+3] cycloaromatization of isopropyl substituted arenes has enabled the on-surface synthesis of arylene-phenylene copolymers, where the surface activates the isopropyl substituents to form phenylene rings by intermolecular coupling. However, the resulting polymers suffered from undesired cross-linking when more than two molecules reacted at a single site. In the manuscript in which this data is discussed we show that such cross-links can be prevented through steric protection by attaching the isopropyl groups to larger arene cores. Upon thermal activation of isopropyl-substituted 8,9-dioxa-8a-borabenzo[fg]tetracene on Au(111), cycloaromatization is observed to occur exclusively between two molecules. The cycloaromatization intermediate formed by the covalent linking of two molecules is prevented from reacting with further molecules by the wide benzotetracene core, resulting in highly selective one-to-one coupling. Our findings extend the versatility of the [3+3] cycloaromatization of isopropyl substituents and point toward steric protection as a powerful concept for suppressing competing reaction pathways in on-surface synthesis.

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External references

Journal reference (Paper where the data is discussed)
A. Kinikar et al. ACS Nanoscience Au (2023) doi:10.1021/acsnanoscienceau.3c00062


MARVEL/P4 SNSF density-functional theory nc-AFM STM on-surface synthesis

Version history:

2023.198 (version v1) [This version] Dec 20, 2023 DOI10.24435/materialscloud:21-aj