Skip to main content

Lund University Publications

LUND UNIVERSITY LIBRARIES

Carbon monoxide ligation at single metal atom sites in a 2D manganese-cobalt coordination network : equilibrium at room temperature

De Col, Michela ; Comini, Danilo ; Baronio, Stefania ; Roondhe, Basant ; Namar, Alessandro ; Bidoggia, Davide ; Scardamaglia, Mattia LU ; Giannozzi, Paolo and Vesselli, Erik (2026) In Journal of Materials Chemistry A
Abstract

We find that CO ligates selectively to nitrogen tetra-coordinated Co(i) single metal atom sites at room temperature in a manganese–cobalt bi-metallic coordination network self-assembled on graphene. The bound state is metastable, determined by pressure-dependent equilibrium conditions between adsorption and desorption, with an upright, end-on bonding geometry (binding energy 0.73 eV). The ligand vibrational hot-band can be populated due to the weak coupling with the substrate. The CO uptake/saturation curve is modeled using Temkin and Hill isotherms, unveiling network-mediated anti-cooperative adsorption. While contributions from direct dipole–dipole interactions and Förster energy transfer are ruled out, the observed anti-cooperativity... (More)

We find that CO ligates selectively to nitrogen tetra-coordinated Co(i) single metal atom sites at room temperature in a manganese–cobalt bi-metallic coordination network self-assembled on graphene. The bound state is metastable, determined by pressure-dependent equilibrium conditions between adsorption and desorption, with an upright, end-on bonding geometry (binding energy 0.73 eV). The ligand vibrational hot-band can be populated due to the weak coupling with the substrate. The CO uptake/saturation curve is modeled using Temkin and Hill isotherms, unveiling network-mediated anti-cooperative adsorption. While contributions from direct dipole–dipole interactions and Förster energy transfer are ruled out, the observed anti-cooperativity originates from network-mediated electronic and magnetic effects. Our findings provide direct insight into ligand dynamics at single metal atom sites in 2D materials and suggest tunable reactivity properties of a 2D biomimetic functional material through its tailored design.

(Less)
Please use this url to cite or link to this publication:
author
; ; ; ; ; ; ; and
organization
publishing date
type
Contribution to journal
publication status
in press
subject
in
Journal of Materials Chemistry A
publisher
Royal Society of Chemistry
external identifiers
  • scopus:105032999176
ISSN
2050-7488
DOI
10.1039/d5ta10405j
language
English
LU publication?
yes
additional info
Publisher Copyright: This journal is © The Royal Society of Chemistry, 2026
id
4e16f5b3-fc66-43fa-9c4b-227699802e6f
date added to LUP
2026-04-27 15:01:52
date last changed
2026-04-27 15:02:49
@article{4e16f5b3-fc66-43fa-9c4b-227699802e6f,
  abstract     = {{<p>We find that CO ligates selectively to nitrogen tetra-coordinated Co(i) single metal atom sites at room temperature in a manganese–cobalt bi-metallic coordination network self-assembled on graphene. The bound state is metastable, determined by pressure-dependent equilibrium conditions between adsorption and desorption, with an upright, end-on bonding geometry (binding energy 0.73 eV). The ligand vibrational hot-band can be populated due to the weak coupling with the substrate. The CO uptake/saturation curve is modeled using Temkin and Hill isotherms, unveiling network-mediated anti-cooperative adsorption. While contributions from direct dipole–dipole interactions and Förster energy transfer are ruled out, the observed anti-cooperativity originates from network-mediated electronic and magnetic effects. Our findings provide direct insight into ligand dynamics at single metal atom sites in 2D materials and suggest tunable reactivity properties of a 2D biomimetic functional material through its tailored design.</p>}},
  author       = {{De Col, Michela and Comini, Danilo and Baronio, Stefania and Roondhe, Basant and Namar, Alessandro and Bidoggia, Davide and Scardamaglia, Mattia and Giannozzi, Paolo and Vesselli, Erik}},
  issn         = {{2050-7488}},
  language     = {{eng}},
  publisher    = {{Royal Society of Chemistry}},
  series       = {{Journal of Materials Chemistry A}},
  title        = {{Carbon monoxide ligation at single metal atom sites in a 2D manganese-cobalt coordination network : equilibrium at room temperature}},
  url          = {{http://dx.doi.org/10.1039/d5ta10405j}},
  doi          = {{10.1039/d5ta10405j}},
  year         = {{2026}},
}