Publications associées à Structure and small molecule activation reactivity of a metallasilsesquioxane of divalent ytterbium

Palladium-based supramolecular assemblies: from complex structures to water-soluble anion-receptors

The combination of palladium salts and bipyridyl ligands can lead to the formation of a large variety of coordination complexes, with different shapes and sizes, displaying a very versatile host-guest chemistry. Increasing their structural complexity remai ...

EPFL2024

Tuning the reactivity of uranium towards small molecules in multimetallic complexes

Nadir Jori

One of the main goals of organometallic chemistry in the last decades was the activation of small molecule in mild reaction conditions. Even though multiple examples of catalytic cycles able to produce fine chemicals from cheap and abundant sources using t ...

EPFL2023

Stabilizing Unusual Oxidation States of Lanthanides in Molecular Complexes: Synthesis, Properties, and Reactivity

Aurélien René Willauer

The chemistry of divalent lanthanides has generated increasing interest in the past years due to their redox properties and unique reaction pathways. Notably, molecular complexes of low-valent lanthanides have been shown to be suitable one-electron reducta ...

EPFL2022

Ligand Effects in Low-Valent Co(I) Clathrochelate Complexes

Kay Severin, Rosario Scopelliti, Farzaneh Fadaei Tirani, Ophélie Marie Planes

Clathrochelate complexes of cobalt are known in the oxidation states I, II, and III. Low-valent Co(I) complexes are highly reactive compounds, and there is only limited knowledge about their structures in the solid state. Herein, we describe the crystallog ...

2021

Luminescent, porous, metal-organic crystals: Design, synthesis, and applications

Fatmah Ebrahim

The work presented in this thesis is focused on the design and discovery of new luminescent, porous, crystalline materials for targeted applications. In particular, we focus on luminescent Metal-Organic Frameworks (MOFs) and Organic Molecules of Intrinsic ...

EPFL2020

Carbon dioxide reduction by lanthanide(iii) complexes supported by redox-active Schiff base ligands

Rosario Scopelliti, Marinella Mazzanti, Davide Toniolo, Nadir Jori

Here we have explored the ability of Schiff bases to act as electron reservoirs and to enable the multi-electron reduction of small molecules by lanthanide complexes. We report the reductive chemistry of the Ln(iii) complexes of the tripodal heptadentate S ...

2020

Colorimetry of Luminescent Lanthanide Complexes

Anne-Sophie Chauvin, Julien Alexandre Andres

Europium, terbium, dysprosium, and samarium are the main trivalent lanthanide ions emitting in the visible spectrum. In this work, the potential of these ions for colorimetric applications and colour reproduction was studied. The conversion of spectral dat ...

2020

Assembly of High-Spin [Fe-3] Clusters by Ligand-Based Multielectron Reduction

Rosario Scopelliti, Marinella Mazzanti, Ivica Zivkovic, Davide Toniolo

The hexanuclear [Na12Fe6(tris-cyclo-salophen)(2)(THF)(14)], 1-THF, and the trinuclear [Na6Fe3(tris-cyclo-salophen)(py)(9)], 1-py, Fe(II) clusters can be easily assembled in one step from the ligand-based reduction of the [FeII(salophen)(THF)] complex. Thes ...

2020

Structure-Property Relationships of Microphase-Separated Metallosupramolecular Polymers

Emad Oveisi, Stephen Schrettl

The structural, thermomechanical, and viscoelastic properties of metallosupramolecular polymers (MSPs) can be controlled through the choice of the multiligand monomer and the nature of the metal salt from which these materials are assembled. This versatili ...

American Chemical Society2020

Delivery of a Masked Uranium(II) by an Oxide-Bridged Diuranium(III) Complex

Marinella Mazzanti, Farzaneh Fadaei Tirani, Dieuwertje Katelijn Modder

Oxide is an attractive linker for building polymetallic complexes that provide molecular models for metal oxide activity, but studies of these systems are limited to metals in high oxidation states. Herein, we synthesized and characterized the molecular an ...

Wiley-VCH Verlag GmbH2021

Carbon dioxide reduction by dinuclear Yb(ii) and Sm(ii) complexes supported by siloxide ligands

Marinella Mazzanti, Farzaneh Fadaei Tirani, Davide Toniolo

Two dinuclear homoleptic complexes of lanthanides(II) supported by the polydentate tris(tertbutoxy) siloxide ligand ([Yb2L4], 1-Yb and [Sm2L4], 1-Sm, (L = (OtBu)3SiO−)) were synthesized in 70–80% yield and 1-Sm was crystallographically characterized. 1-Yb ...

2019

Molecular Complex of Tb in the +4 Oxidation State

Rosario Scopelliti, Marinella Mazzanti, Ivica Zivkovic

Lanthanides (Ln) usually occur in the +3, or more recently the +2, oxidation states. The only example of an isolated molecular Ln(4+) so far remains Ce4+. Here we show that the +4 oxidation state is also accessible in a molecular compound of terbium as dem ...

2019

Rh-I, Ir-III ,and Co-III Complexes with Atropchiral Biaryl Cyclopentadienyl Ligands: Syntheses, Structures, and Catalytic Activities

Nicolai Cramer, Gints Smits, Coralie Danielle Annick Duchemin

Chiral cyclopentadienyl (Cp-x) group 9 metal complexes have become versatile catalysts for a variety of efficient enantioselective C-H functionalizations. Atropchiral binaphthyl-derived Cp-x ligands having tuning options at the 3,3'-positions present a rob ...

2019

Small Molecule Activation by Multimetallic Uranium Complexes

Marta Falcone

The development of new processes for the selective and sustainable transformation of abundant small molecules constitutes one of the major research areas in inorganic and organometallic chemistry. These molecules as CO2, CO, N2 and H2 are abundant reservoi ...

EPFL2019

Features of proteolytic properties of tetraphenylporphyrin complex with lanthanide group metals

Demetallation of metalloporphyrin molecules is one of the essential degradation reactions in photosynthesis. The effect of metalloporphyrin nature on removal of central metals from tetraphenylporphyrin complexes based on lanthanide group metals (Dy, Er, Lu ...

2018

Ligand and Metal Based Multielectron Redox Chemistry of Cobalt Supported by Tetradentate Schiff Bases

Rosario Scopelliti, Marinella Mazzanti, Julie Renée Michelle Andrez

We have investigated the influence of bound cations on the reduction of cobalt complexes of redox active ligands and explored the reactivity of reduced species with CO2. The one electron reduction of [CoII(Rsalophen)] with alkali metals (M = Li, Na, K) lea ...

2017

Magnetic properties of surface-adsorbed single rare earth atoms, molecules, and atomic scale clusters

Aparajita Singha

This thesis presents combined experimental and theoretical investigations of nanoscale, surface-supported magnets based on rare earths (RE) to understand and control the magnetic properties down to the scale of single atoms. We present the effects of adato ...

EPFL2017

4 f occupancy and magnetism of rare-earth atoms adsorbed on metal substrates

Harald Brune, Pietro Gambardella, Stefano Rusponi, Sebastian Stepanow, Fabio Donati, Aparajita Singha, Jan Gui-Hyon Dreiser, Christian Wäckerlin, Romana Baltic

We report x-ray absorption spectroscopy and x-ray magnetic circular dichroism measurements as well as multiplet calculations for Dy, Ho, Er, and Tm atoms adsorbed on Pt(111), Cu(111), Ag(100), and Ag(111). In the gas phase, all four elements are divalent a ...

Amer Physical Soc2017

Synthesis of molecular complexes for small molecule activation

Julie Renée Michelle Andrez

The redox chemistry of f-elements is drawing the attention of inorganic chemists due to their unusual reaction pathways. Notably low-valent f-element complexes have been shown to be able to activate small molecules such as CO2 and N2 in mild conditions. Co ...

EPFL2016

Water exchange studies of lanthanide complexes and aqua ions

Shima Karimi

Complexes of lanthanide (III) ions have been used in structural studies of biomolecules and as contrast agents (CA). Clinically approved CAs have only one water molecule in their first coordination sphere. Structure and water exchange rate of these complex ...

EPFL2016