TY - JOUR
T1 - One-dimensional heterocyclic carbene–Au metal–organic frameworks bridging ultra-high vacuum models and scalable liquid-phase growth
AU - Cielo, Leonardo
AU - Cattelan, Mattia
AU - Schio, Luca
AU - Longo, Leonardo
AU - Grillo, Federico
AU - Qie, Boyu
AU - Wang, Ziyi
AU - Floreano, Luca
AU - Baddeley, Christopher J.
AU - Sedona, Francesco
AU - Tubaro, Cristina
AU - Fischer, Felix R.
AU - Agnoli, Stefano
N1 - Funding: The authors acknowledge financial support under the National Recovery and Resilience Plan (NRRP), Mission 4, Component 2, Investment 1.1, by the Italian Ministry of University and Research (MUR), funded by the European Union – NextGenerationEU– Project Title “Microscopic approach to Understand Synergies in Electrocatalysis” - Project No. 2022E5L4Y2 - CUP: C53D23003780006. We acknowledge support from Project C2 chemical complexity (CUP: C93C22009260001) under the MUR program “Dipartimenti di Eccellenza 2023-2027”. Financial support was provided by the US Department of Energy (DOE), Office of Science, Basic Energy Sciences (BES), Materials Sciences and Engineering Division under contract DE-AC02-05-CH11231 (Nanomachine program KC1203) (STM imaging) and contract DE-SC0023105 (molecular design and synthesis). The University of Padova is acknowledged for financial support through the grant #01BIRD2022-UNIPD (MUSYCA) and joint call in education and research 2024 University of Padova and University of St. Andrews “Surface Synthesized Carbene Networks for Electrocatalysis”.We acknowledge financial support under the National Recovery and Resilience Plan (NRRP), Mission 4, Component 2, Investment 1.1, by the Italian Ministry of University and Research (MUR), funded by the European Union – NextGenerationEU– Project Title “Microscopic approach to Understand Synergies in Electrocatalysis” - Project No. 2022E5L4Y2 - CUP: C53D23003780006. We acknowledge support from Project C2 chemical complexity (CUP: C93C22009260001) under the MUR program “Dipartimenti di Eccellenza 2023-2027”. Financial support was provided by the US Department of Energy (DOE), Office of Science, Basic Energy Sciences (BES), Materials Sciences and Engineering Division under contract DE-AC02-05-CH11231 (Nanomachine program KC1203) (STM imaging) and contract DE-SC0023105 (molecular design and synthesis). The University of Padova is acknowledged for financial support through the grant #01BIRD2022-UNIPD (MUSYCA) and joint call in education and research 2024 University of Padova and University of St. Andrews “Surface Synthesized Carbene Networks for Electrocatalysis”.
PY - 2025/11/24
Y1 - 2025/11/24
N2 - The controlled design of molecule–metal interfaces is central to the development of functional nanomaterials for catalysis, sensing, and molecular electronics. Here we show that the adsorption of a Janus-type diimidazolium precursor on gold yields one-dimensional (1D) N-heterocyclic carbene (NHC)–Au–NHC metal organic frameworks (MOFs) featuring positively charged gold nodes. Using synchrotron X-ray photoemission spectroscopy (XPS), near edge X-ray adsorption fine structure (NEXAFS) spectroscopy and scanning tunnelling microscopy (STM), we demonstrate that thermal activation promotes counterion removal and drives the formation of extended 1D arrays, characterized by ∼1.0 nm Au–Au spacing and adatom densities up to 0.6 atom nm−2 (∼4% of surface atoms). Importantly, we translate this ultra-high vacuum (UHV) benchmark into a scalable solution-phase protocol in ethanol, enabling 1D-MOF growth under mild, base-free, open-air conditions. The resulting films retain structural and electronic signatures of UHV-grown systems, bridging model studies and practical synthesis. This approach establishes NHC–metal frameworks as accessible, tunable platforms for catalysis and materials design.
AB - The controlled design of molecule–metal interfaces is central to the development of functional nanomaterials for catalysis, sensing, and molecular electronics. Here we show that the adsorption of a Janus-type diimidazolium precursor on gold yields one-dimensional (1D) N-heterocyclic carbene (NHC)–Au–NHC metal organic frameworks (MOFs) featuring positively charged gold nodes. Using synchrotron X-ray photoemission spectroscopy (XPS), near edge X-ray adsorption fine structure (NEXAFS) spectroscopy and scanning tunnelling microscopy (STM), we demonstrate that thermal activation promotes counterion removal and drives the formation of extended 1D arrays, characterized by ∼1.0 nm Au–Au spacing and adatom densities up to 0.6 atom nm−2 (∼4% of surface atoms). Importantly, we translate this ultra-high vacuum (UHV) benchmark into a scalable solution-phase protocol in ethanol, enabling 1D-MOF growth under mild, base-free, open-air conditions. The resulting films retain structural and electronic signatures of UHV-grown systems, bridging model studies and practical synthesis. This approach establishes NHC–metal frameworks as accessible, tunable platforms for catalysis and materials design.
KW - NHC–Au–NHC 1D-MOFs
KW - Gold adatoms
KW - UHV-to-solution synthesis translation
KW - Synchrotron spectroscopies
KW - STM
UR - https://www.scopus.com/pages/publications/105022425862
U2 - 10.1016/j.apsusc.2025.165322
DO - 10.1016/j.apsusc.2025.165322
M3 - Article
AN - SCOPUS:105022425862
SN - 0169-4332
VL - 720
JO - Applied Surface Science
JF - Applied Surface Science
IS - Part C
M1 - 165322
ER -