Iodine versus Bromine Functionalization for Bottom-Up Graphene Nanoribbon Growth: Role of Diffusion

Bronner, Christopher; Marangoni, Tomas; Rizzo, Daniel J.; Durr, Rebecca A.; Jorgensen, Jakob Holm; Fischer, Felix R.; Crommie, Michael F.

doi:10.1021/acs.jpcc.7b02896

Title: Iodine versus Bromine Functionalization for Bottom-Up Graphene Nanoribbon Growth: Role of Diffusion

Journal Article · 07 August 2017 · Journal of Physical Chemistry. C

DOI: https://doi.org/10.1021/acs.jpcc.7b02896 · OSTI ID:1436639

^[1]; Marangoni, Tomas ^[2]; Rizzo, Daniel J. ^[1]; Durr, Rebecca A. ^[2]; Jorgensen, Jakob Holm ^[3];

^[4]; Crommie, Michael F. ^[5]

Univ. of California, Berkeley, CA (United States). Dept. of Physics
Univ. of California, Berkeley, CA (United States). Dept. of Chemistry
Aarhus Univ. (Denmark). iNANO. Dept. of Physics and Astronomy
Univ. of California, Berkeley, CA (United States). Dept. of Chemistry; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division. Kavli Energy NanoSciences Inst.
Univ. of California, Berkeley, CA (United States). Dept. of Physics; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division. Kavli Energy NanoSciences Inst.

Deterministic bottom-up approaches for synthesizing atomically well-defined graphene nanoribbons (GNRs) largely rely on the surface-catalyzed activation of selected labile bonds in a molecular precursor followed by step-growth polymerization and cyclodehydrogenation. While the majority of successful GNR precursors rely on the homolytic cleavage of thermally labile C–Br bonds, the introduction of weaker C–I bonds provides access to monomers that can be polymerized at significantly lower temperatures, thus helping to increase the flexibility of the GNR synthesis process. Scanning tunneling microscopy imaging of molecular precursors, activated intermediates, and polymers resulting from stepwise thermal annealing of both Br and I substituted precursors for chevron GNRs reveals that the polymerization of both precursors proceeds at similar temperatures on Au(111). Finally, this surprising observation is consistent with diffusion-controlled polymerization of the surface-stabilized radical intermediates that emerge from homolytic cleavage of either the C–Br or the C–I bonds.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); Office of Naval Research (ONR) (United States); Academy of Sciences Leopoldina (Germany)

Grant/Contract Number:: AC02-05CH11231; SC0010409

OSTI ID:: 1436639

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 34 Vol. 121; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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