Universität zu Köln

Kraus, Stefan ORCID: 0000-0002-5987-746X, Herman, Alexander, Huttmann, Felix, Kramer, Christian, Amsharov, Konstantin, Tsukamoto, Shigeru ORCID: 0000-0001-5271-9277, Wende, Heiko ORCID: 0000-0001-8395-3541, Atodiresei, Nicolae and Michely, Thomas ORCID: 0000-0003-1657-1847 (2022). Selecting the Reaction Path in On-Surface Synthesis through the Electron Chemical Potential in Graphene. J. Am. Chem. Soc., 144 (24). S. 11003 - 11010. WASHINGTON: AMER CHEMICAL SOC. ISSN 1520-5126

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Abstract

The organometallic on-surface synthesis of the eight-membered sp(2) carbon-based ring cyclooctatetraene (C8H8, Cot) with the neighboring rare-earth elements ytterbium and thulium yields fundamentally different products for the two lanthanides, when conducted on graphene (Gr) close to the charge neutrality point. Sandwich-molecular YbCot wires of more than 500 angstrom length being composed of an alternating sequence of Yb atoms and upright-standing Cot molecules result from the on-surface synthesis with Yb. In contrast, repulsively interacting TmCot dots consisting of a single Cot molecule and a single Tm atom result from the on-surface synthesis with Tm. While the YbCot wires are bound through van der Waals interactions to the substrate, the dots are chemisorbed to Gr via the Tm atoms being more electropositive compared to Yb atoms. When the electron chemical potential in Gr is substantially raised (n-doping) through backside doping from an intercalation layer, the reaction product in the synthesis with Tm can be tuned to TmCot sandwich-molecular wires rather than TmCot dots. By use of density functional theory, it is found that the reduced electronegativity of Gr upon n-doping weakens the binding as well as the charge transfer between the reaction intermediate TmCot dot and Gr. Thus, the assembly of the TmCot dots to long TmCot sandwich-molecular wires becomes energetically favorable. It is thereby demonstrated that the electron chemical potential in Gr can be used as a control parameter in an organometallic on-surface synthesis to tune the outcome of a reaction.

Item Type:	Journal Article
Creators:	Creators Email ORCID ORCID Put Code Kraus, Stefan UNSPECIFIED orcid.org/0000-0002-5987-746X UNSPECIFIED Herman, Alexander UNSPECIFIED UNSPECIFIED UNSPECIFIED Huttmann, Felix UNSPECIFIED UNSPECIFIED UNSPECIFIED Kramer, Christian UNSPECIFIED UNSPECIFIED UNSPECIFIED Amsharov, Konstantin UNSPECIFIED UNSPECIFIED UNSPECIFIED Tsukamoto, Shigeru UNSPECIFIED orcid.org/0000-0001-5271-9277 UNSPECIFIED Wende, Heiko UNSPECIFIED orcid.org/0000-0001-8395-3541 UNSPECIFIED Atodiresei, Nicolae UNSPECIFIED UNSPECIFIED UNSPECIFIED Michely, Thomas UNSPECIFIED orcid.org/0000-0003-1657-1847 UNSPECIFIED
URN:	urn:nbn:de:hbz:38-681579
DOI:	10.1021/jacs.2c04359
Journal or Publication Title:	J. Am. Chem. Soc.
Volume:	144
Number:	24
Page Range:	S. 11003 - 11010
Date:	2022
Publisher:	AMER CHEMICAL SOC
Place of Publication:	WASHINGTON
ISSN:	1520-5126
Language:	English
Faculty:	Unspecified
Divisions:	Unspecified
Subjects:	no entry
Uncontrolled Keywords:	Keywords Language SANDWICH COMPLEXES; TRANSFER CHEMISTRY; ADSORPTION; CATALYSIS; CLUSTERS; EXCHANGE Multiple languages Chemistry, Multidisciplinary Multiple languages
URI:	http://kups.ub.uni-koeln.de/id/eprint/68157