Kinetic Isotope Effect in the Radical Step-Growth Termination of On-Surface Synthesized Graphene NanoribbonsShow others and affiliations
2025 (English)In: Nano Letters, ISSN 1530-6984, E-ISSN 1530-6992, Vol. 25, no 23, p. 9450-9455Article in journal (Refereed) Published
Abstract [en]
Bottom-up on-surface synthesis has emerged as a versatile tool to access and finely tune the electronic structure of nanographenes. The controlled generation of reactive intermediates catalyzed and stabilized by a supporting substrate has enabled the design, assembly, and characterization of a wide range of exotic tailor-made quantum materials. Even under these tightly controlled conditions, the growth of extended structures remains limited by termination processes and undesired side reactions. Here, we identify an H atom transfer as one principal contributor to the radical step growth termination that limits the on-surface growth of N = 7 armchair graphene nanoribbons (7-AGNRs) on Au(111) surfaces. Analysis of 7-AGNR lengths grown from protiated and deuterated molecular precursors reveals a primary kinetic isotope effect of KIE similar to 1.4. First-principles density functional theory calculations suggest that a concerted H atom transfer mechanism that involves the breaking of a C-H/D bond in the transition state is associated with radical chain termination.
Place, publisher, year, edition, pages
AMER CHEMICAL SOC , 2025. Vol. 25, no 23, p. 9450-9455
Keywords [en]
on-surface polymerization; graphene nanoribbon synthesis; length distribution; kinetic isotope effect; step growth termination
National Category
Materials Chemistry
Identifiers
URN: urn:nbn:se:liu:diva-214441DOI: 10.1021/acs.nanolett.5c02047ISI: 001500766200001PubMedID: 40455422Scopus ID: 2-s2.0-105007341317OAI: oai:DiVA.org:liu-214441DiVA, id: diva2:1966505
Note
Funding Agencies|Office of Naval Research [DE-AC02-05-CH11231, KC1203, DE-SC0023105]; US Department of Energy (DOE), Office of Science, Basic Energy Sciences (BES), Materials Sciences and Engineering Division [N00014-20-1-2824]; Office of Naval Research; Heising-Simons Faculty Fellows Program at UC Berkeley [SFO-Mat-LiU 2009-00971]; Swedish Government Strategic Research Area in Materials Science on Advanced Functional Materials at Linkoping University [2022-06725]; Swedish Research Council [S10OD024998]; National Institutes of Health (NIH)
2025-06-102025-06-102026-03-05Bibliographically approved