Lanthanide(III)-binding peptides and proteins: coordination properties and applications
Falcone E., Mathieu E., Hureau C.
Chem. Soc. Rev. 2025,
10.1039/D4CS01148A – hal-05273561

Lanthanides play a crucial role in modern medicine and technology as well as in the metabolism of methylotrophic bacteria. In this context, the research on lanthanide-binding peptides and proteins is an active and rapidly developing field. This comprehensive and critical review focuses on the structural, thermodynamic (affinity and selectivity) and kinetic parameters governing the interaction of Ln³⁺ ions with different peptides and proteins, including both naturally occurring and de novo-designed scaffolds. It thus provides guidelines and future directions for the rational design of Ln-binding peptides and proteins with suitable features for the main applications explored to date, including luminescent sensing, magnetic resonance imaging, Ln separation and recovery and Ln-based (photo)-catalysis.

Contact:
Enrico Falcone, Enrico.falcone@lcc-toulouse.fr

Spin crossover particle shielding upon grinding in thermoplastic polyurethane composites.

A. Trapali, J. F. Meunier, M. Baltas, L. Salmon*, A. Bousseksou*.
Chem. Commun., 2025, 61, 16190-16193.
https://doi.org/10.1039/D5CC04205D

Ball milling experiments were conducted on spin crossover (SCO) powder and SCO@polyurethane composite samples. The study reveals that the presence of the TPU matrix acts as a shield for the SCO particles upon grinding, precluding their deactivation. This result is encouraging for the integration of SCO materials into devices.

Contacts:
Lionel Salmon lionel.salmon@lcc-toulouse.fr
Azzedine Bousseksou azzedine.bousseksou@lcc-toulouse.fr

Elucidating the Correlation Between the Redox Potential, Spin State, and Crystal Structure in a Series of Ferrous Complexes with Redox-Active Ligands.

Livia Getzner,  Yasmine Remili,  Zakaria Ziani,  Laure Vendier,  William Nicolazzi,  Aurelian Rotaru,  Haizhu Yu,  Gábor Molnár,  Saioa Cobo,  Azzedine Bousseksou.
Angew. Chem. Int. Ed. 2025, e202506965.
https://doi.org/10.1002/anie.202506965

A series of Fe(II) Hofmann-type clathrates with redox-active ligands reveals a bell-shaped relationship between redox potential and spin crossover temperature.
This work uncovers how electronic ligand tuning modulates spin state, crystal symmetry, and electron transfer, rationalized through Marcus theory.

Contacts:
Saioa Cobo  saioa.cobo@lcc-toulouse.fr
Azzedine Bousseksou azzedine.bousseksou@lcc-toulouse.fr

Unlike lanthanide ions, 1^st-order spin-orbit coupling (SOC) is cancelled by the ligand field for transition metal ions, and achieving high magnetic anisotropy is generally considered the Holy Grail for these ions. Results obtained with Fe(II) show that a contribution from first-order SOC coupling is not confined to low-coordination number complexes but can be implemented in a pentagonal bipyramid complexes (figure) by proper chemical design. This is confirmed by theoretical calculations and experimental magnetic behaviors consistent with the existence of large magnetic anisotropy, most salient feature being the SMM behaviors with large energy barriers for magnetization reversal. The observation of such a behavior without an applied static magnetic field is quite unique for a mononuclear 3d complex.

pH-Controlled Gliding Motions in Pillar[5]arene-Containing Molecular Shuttles.

Becharguia, N., Nierengarten, I., Sournia-Saquet, A., Wasielewski, E., Abidi, R., Delavaux-Nicot, B. and Nierengarten, J.-F.
ChemistryEurope. 2025, 3: e202400115.
https://doi.org/10.1002/ceur.202400115

Researchers from “Laboratoire de chimie de coordination (LCC Toulouse)” and “Laboratoire de chimie des matériaux moléculaires (UNISTRA Strasbourg)” have designed molecular shuttles and are able to control their movement. These molecular machines use a ring-shaped molecule, called pillar[5]arene, which can glide along an axis made up of two distinct stations.

What makes these shuttles unique is that they respond to their environment:

• In an acidic environment (low pH), the ring can freely glide along the entire length of the rail.
• In a neutral environment, such molecular motions are limited over the decyl station.

The ring can also be blocked on a specific part of the rail (the decyl station) by modifying the protonated molecule using electrochemical oxidation.
This system demonstrates that it is possible to precisely control the motion of molecular components, opening new possibilities in nanotechnology and smart materials.

Contact:
Béatrice Delavaux-Nicot beatrice.delavaux-nicot@lcc-toulouse.fr
Jean-François Nierengarten nierengarten@unistra.fr
Iwona Nierengarten iosinska@unistra.fr

Infuzide : A Promising New Molecule Against Multidrug-Resistant Bacteria

Influence of Capping Ligands on Metal-Nanoparticle-Driven Hydrogen Evolution and CO2 Reduction Reactions

Nuria Romero, Karine Philippot

ABSTRACT
This chapter looks into the influence of the functionalization of the surface of metal nanoparticles (MNPs) with ligands on their catalytic performance in two crucial reactions, the hydrogen evolution reaction (HER) and the CO2 reduction reaction (CO2RR). The birth of the surface functionalization of MNPs with ligands was greatly inspired by the advanced knowledge accumulated on molecular metal catalysts, whose physical and chemical properties can be tuned by coordinating appropriate ligands to the metal active center. This field of research has profited from the progress in the synthetic methods for the generation of MNPs and the evolution of the spectroscopic and analytical techniques for their exhaustive characterization, as well as the improvement of the computational techniques. Relevant examples will illustrate how the functionalization of the surface of MNPs allow to modulate the energy profile of catalytic intermediate species through electronic effects and regulate the product selectivity through hydrophobic/hydrophilic effects. Another key parameter is the tuning of the number of surface-active sites as a function of the metal to ligand ratio and the chemical nature of the coordinating ligand. Furthermore, in some peculiar cases, second coordination sphere effects have even been described in analogy to biological enzymes.

Contact:
Karine Philippot Karine.Philippot(at)lcc-toulouse.fr

Reference:
Influence of Capping Ligands on Metal-Nanoparticle-Driven Hydrogen Evolution and CO2 Reduction Reactions
Martí G., Lozano-Roche A., Romero N., Francàs L., Philippot K., Bofill R., García-Antón J., Sala X.
in Topics in Organometallic Chemistry. Surface Functionalized Metal Catalysts, L. M. Martínez-Prieto (Ed.), Springer International Publishing: Cham, 2024, vol. 75, pp. 105-132. (978-3-031-73841-8).
https://doi.org/10.1007/3418_2024_116
https://hal.science/hal-04821235

Lawsone

Molecule of the week ‘MOTW’ is a popular feature on the American Chemical Society’s website.

A publication concerning the reaction of lawsone with various aldehydes and isocyanides by teams R and V in collaboration with the University of Tartu (Estonia) is cited in “ACS molecule of the week”!

Read the article about Lawsone on ACS molecule of the week
Read the publication cited: Reaction of lawsone with various aldehydes and isocyanides

Contact: Michel Baltas  Michel.Baltas(at)lcc-toulouse.fr