Sterically selective [3+3] cycloaromatization in the on-surface synthesis of nanographenes
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{
"revision": 7,
"id": "2026",
"created": "2023-12-14T09:18:07.161583+00:00",
"metadata": {
"doi": "10.24435/materialscloud:21-aj",
"status": "published",
"title": "Sterically selective [3+3] cycloaromatization in the on-surface synthesis of nanographenes",
"mcid": "2023.198",
"license_addendum": null,
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"keywords": [
"MARVEL/P4",
"SNSF",
"density-functional theory",
"nc-AFM",
"STM",
"on-surface synthesis"
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"conceptrecid": "2025",
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"references": [
{
"type": "Journal reference",
"doi": "10.1021/acsnanoscienceau.3c00062",
"comment": "Paper where the data is discussed",
"citation": "A. Kinikar et al. ACS Nanoscience Au (2023)"
}
],
"publication_date": "Dec 20, 2023, 13:00:50",
"license": "Creative Commons Attribution 4.0 International",
"id": "2026",
"description": "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.",
"version": 1,
"contributors": [
{
"email": "amogh.kinikar@empa.ch",
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"Empa, Swiss Federal Laboratories for Materials Science and Technology, 8600 D\u00fcbendorf (Switzerland)"
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"familyname": "Kinikar",
"givennames": "Amogh"
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{
"affiliations": [
"Max Planck Institute for Polymer Research, 55128 Mainz (Germany)"
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"familyname": "Wang",
"givennames": "Xiao-Ye"
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{
"affiliations": [
"Empa, Swiss Federal Laboratories for Materials Science and Technology, 8600 D\u00fcbendorf (Switzerland)"
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"familyname": "Di Giovannantonio",
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"affiliations": [
"Empa, Swiss Federal Laboratories for Materials Science and Technology, 8600 D\u00fcbendorf (Switzerland)"
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"familyname": "I. Urgel",
"givennames": "Jos\u00e9"
},
{
"affiliations": [
"State Key Laboratory of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin 300071 (China)"
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"familyname": "Liu",
"givennames": "Pengcai"
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"familyname": "Eimre",
"givennames": "Kristjan"
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{
"affiliations": [
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"familyname": "Pignedoli",
"givennames": "Carlo Antonio"
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{
"affiliations": [
"Empa, Swiss Federal Laboratories for Materials Science and Technology, 8600 D\u00fcbendorf (Switzerland)"
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"familyname": "Stolz",
"givennames": "Samuel"
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"affiliations": [
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"familyname": "Bommert",
"givennames": "Max"
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"familyname": "Mishra",
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"Empa, Swiss Federal Laboratories for Materials Science and Technology, 8600 D\u00fcbendorf (Switzerland)"
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"familyname": "Widmer",
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"Max Planck Institute for Polymer Research, 55128 Mainz (Germany)"
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"familyname": "Qiu",
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"Empa, Swiss Federal Laboratories for Materials Science and Technology, 8600 D\u00fcbendorf (Switzerland)"
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"familyname": "Narita",
"givennames": "Akimitsu"
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"affiliations": [
"Max Planck Institute for Polymer Research, 55128 Mainz (Germany)"
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"familyname": "M\u00fcllen",
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"familyname": "Ruffieux",
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"affiliations": [
"Empa, Swiss Federal Laboratories for Materials Science and Technology, 8600 D\u00fcbendorf (Switzerland)"
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"familyname": "Fasel",
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],
"edited_by": 576
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"updated": "2023-12-20T12:00:50.334202+00:00"
}