Journal Article

FZJ-2026-03827

http://join2-wiki.gsi.de/foswiki/pub/Main/Artwork/join2_logo100x88.png Highly Structure‐Selective On‐Surface Synthesis of Isokekulene Versus Kekulene

Ruan, Z. ; Fan, Q. ; Reichmann, A. ; Kang, F. ; Naumann, T. ; Werner, S. ; Kleykamp, O. ; Martinez-Castro, J.FZJ* ; Lüpke, F.FZJ* ; Haags, A.FZJ* ; Bocquet, F. C.FZJ* ; Kumpf, C.FZJ* ; Soubatch, S.FZJ* ; Sundermeyer, J. ; Puschnig, P. ; Tautz, F. S.FZJ* ; Gottfried, J. M. ; Wenzel, S. (Corresponding author)FZJ*

2025
Wiley-VCH Weinheim

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Please use a persistent id in citations: doi:10.1002/ange.202509932  doi:10.34734/FZJ-2026-03827

Abstract: The role of different facets of metal nanoparticles in steering reaction pathways is crucial for the design of heterogeneous catalysts with superior selectivity. As a prominent class of reactions, transition-metal-catalyzed carbon-hydrogen (C─H) bond activation is widely used for the synthesis of base chemicals, modern organic materials, and pharmaceuticals. Here, we report orthogonal selectivity in intramolecular cyclodehydrogenation of a nonplanar cyclic precursor steered by different facets of a copper single crystal. On the Cu(110) surface, the previously unknown cycloarene isokekulene forms with a high selectivity of 92%, whereas reaction on the Cu(111) surface exclusively yields kekulene (>99%). Combining scanning tunneling microscopy with CO-functionalized tips and density functional theory, we identify two adsorption geometries of the precursor, which react to the respective products. Isokekulene adopts two nonplanar adsorption configurations and exhibits strong molecule-substrate interactions, explaining its preferential formation on Cu(110). This combined in-solution and on-surface synthesis approach represents an alternative route for the highly selective synthesis of molecules that are challenging to synthesize and process via conventional methods.

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Contributing Institute(s):

1. Quantum Nanoscience (PGI-3)

Research Program(s):

1. 5213 - Quantum Nanoscience (POF4-521) (POF4-521)
2. SFB 1083 A12 - Struktur und Anregungen von hetero-epitaktischen Schichtsystemen aus schwach wechselwirkenden 2D-Materialien und molekularen Schichten (A12) (385975694) (385975694)
3. DFG project G:(GEPRIS)511561801 - Manipulierung von 2D Supraleitung und Majorana Zuständen auf der Nanoskala (511561801) (511561801)
4. ML4Q - Machine Learning for Quantum (101120240) (101120240)

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Database coverage:
; ; ; DEAL Wiley ; Ebsco Academic Search ; Nationallizenz ; SCOPUS

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