Single Ni Atoms Drive Carboxyl Deprotonation in Metal–Organic Chains

Understanding how charge transfer and ligand activation processes govern metal-organic coordination at surfaces is crucial for controlling on-surface synthesis and the formation of low-dimensional architectures. Here, we show that Ni promotes the deprotonation of the carboxyl groups of terephthalic acid (TPA) on Ag(100), leading to the formation of linear metal-organic coordination chains. Scanning tunneling microscopy reveals that these chains emerge from preassembled hydrogen-bonded TPA stripes. X-ray photoelectron spectroscopy identifies stabilization of the Ni centers in the Ni(I) oxidation state through a single-electron charge transfer process, accompanied by the formation of deprotonated carboxylate species. Valence band spectroscopy reveals a coordination-induced electronic reorganization between Ni and TPA through the emergence of hybrid states, in agreement with complementary theoretical modeling. Together, these findings identify charge-transfer-driven deprotonation as the central mechanism governing the formation of linear metal-organic chains.

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Publication Details

Journal
ACS Nano
Published
2026-04-17
DOI
https://doi.org/10.1021/acsnano.6c01444
Primary Topic
Organometallic Complex Synthesis and Catalysis
Type
article
Field-Weighted Citation Impact
0.00

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article

Single Ni Atoms Drive Carboxyl Deprotonation in Metal–Organic Chains

Giovanni Zamborlini, Daniel Baranowski, Dominik Brandstetter, Matteo Jugovac et al.
ACS Nano
Organometallic Complex Synthesis and Catalysis
article

Single Ni Atoms Drive Carboxyl Deprotonation in Metal–Organic Chains

Giovanni Zamborlini, Daniel Baranowski, Dominik Brandstetter, Matteo Jugovac, Martin Sterrer, Andreas Windischbacher, Vitaliy Feyer, Iulia Cojocariu, Yan Yan Grisan Qiu, Maximilian Lasshofer, Claus Michael Schneider, Simone Mearini, Fabian Auer
article en

Abstract

Understanding how charge transfer and ligand activation processes govern metal-organic coordination at surfaces is crucial for controlling on-surface synthesis and the formation of low-dimensional architectures. Here, we show that Ni promotes the deprotonation of the carboxyl groups of terephthalic acid (TPA) on Ag(100), leading to the formation of linear metal-organic coordination chains. Scanning tunneling microscopy reveals that these chains emerge from preassembled hydrogen-bonded TPA stripes. X-ray photoelectron spectroscopy identifies stabilization of the Ni centers in the Ni(I) oxidation state through a single-electron charge transfer process, accompanied by the formation of deprotonated carboxylate species. Valence band spectroscopy reveals a coordination-induced electronic reorganization between Ni and TPA through the emergence of hybrid states, in agreement with complementary theoretical modeling. Together, these findings identify charge-transfer-driven deprotonation as the central mechanism governing the formation of linear metal-organic chains.

ACS NanoVol. 20(16)
University of Trieste (IT), University of Graz (AT), Forschungszentrum Jülich (DE), Ernst Ruska Centre (DE), Elettra-Sincrotrone Trieste S.C.p.A. (IT), Grunberger Diabetes Institute (US), Nawi Graz (AT), University of Duisburg-Essen (DE), University of California, Davis (US)
Deutsche Forschungsgemeinschaft, HORIZON EUROPE European Research Council
Openalex Percentile: Top 21%
Organometallic Complex Synthesis and Catalysis
DOIOpen Access PDFOpenAlex
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