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The Role of Kinetics versus Thermodynamics in Surface-Assisted Ullmann Coupling on Gold and Silver Surfaces
Tech Univ Munich, Germany; Deutsch Museum, Germany.
Tech Univ Munich, Germany; Diamond Light Source, England.
Tech Univ Munich, Germany.
Tech Univ Munich, Germany; Deutsch Museum, Germany.
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2019 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 141, no 12, p. 4824-4832Article in journal (Refereed) Published
Abstract [en]

Surface-assisted Ullmann coupling is the workhorse of on-surface synthesis. Despite its obvious relevance, many fundamental and mechanistic aspects remain elusive. To shed light on individual reaction steps and their progression with temperature, temperature-programmed X-ray photoelectron spectroscopy (TP-XPS) experiments are performed for a prototypical model system. The activation of the coupling by initial dehalogenation is tracked by monitoring Br 3d core levels, whereas the C 1s signature is used to follow the emergence of metastable organometallic intermediates and their conversion to the final covalent products upon heating in real time. The employed 1,3,5-tris(4-bromophenyl)benzene precursor is comparatively studied on Ag(111) versus Au(111), whereby intermolecular bonds and network topologies are additionally characterized by scanning tunneling microscopy (STM). Besides the well-comprehended differences in activation temperatures for debromination, the thermal progression shows marked differences between the two surfaces. Debromination proceeds rapidly on Ag(111), but is relatively gradual on Au(111). While on Ag(111) debromination is well explained by first-order reaction kinetics, thermodynamics prevail on Au(111), underpinned by a close agreement between experimentally deduced and density functional theory (DFT) calculated reaction enthalpies. Thermodynamically controlled debromination on Au(111) over a large temperature range implies an unexpectedly long lifetime of surface-stabilized radicals prior to covalent coupling, as corroborated by TP-XPS of C is core levels. These insights are anticipated to play an important role regarding our ability to rationally synthesize atomically precise low-dimensional covalent nanostructures on surfaces.

Place, publisher, year, edition, pages
AMER CHEMICAL SOC , 2019. Vol. 141, no 12, p. 4824-4832
National Category
Materials Chemistry
Identifiers
URN: urn:nbn:se:liu:diva-156570DOI: 10.1021/jacs.8b11473ISI: 000462950800009PubMedID: 30817138OAI: oai:DiVA.org:liu-156570DiVA, id: diva2:1315854
Note

Funding Agencies|DFG through the Nanosystems Initiative Munich (NIM); Munich Centre for Advanced Photonics (MAP); Helmholtz-Zentrum Berlin; Marie Curie Intra-European Fellowship (project SiliNano) [626397]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University (Faculty Grant SFO-Mat-LiU) [2009 00971]; Swedish Research Council

Available from: 2019-05-15 Created: 2019-05-15 Last updated: 2019-05-15

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