Publications related to Organolanthanide chemistry

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

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

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

Taking lanthanides out of isolation: tuning the optical properties of metal-organic frameworks

Berend Smit, Kevin Sivula, Nestor Guijarro Carratala, Kyriakos Stylianou, Gloria Capano, Andrzej Gladysiak, Christopher Patrick Ireland, Maria Fumanal Quintana, Stavroula Kampouri, Davide Tiana, Samantha Lynn Anderson, Muhammad Aiman Bin Rahmanudin Hamdan

Metal organic frameworks (MOFs) are increasingly used in applications that rely on the optical and electronic properties of these materials. These applications require a fundamental understanding on how the structure of these materials, and in particular t ...

2020

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

Influence of Symmetry on the Luminescence and Radiative Lifetime of Nine-Coordinate Europium Complexes

Rosario Scopelliti, Jean-Claude Bünzli, Svetlana Eliseeva

Homoleptic mononuclear nine-coordinate lanthanum(III) and europium(III) tris-complexes [Ln(N^N^O)3]·nH2O with two tridentate N-benzyl-benzimidazole pyridine-2-carboxylates exhibit a rare C3-symmetry of the lanthanide coordination polyhedron in the solid st ...

Amer Chemical Soc2015

Lanthanide(II) Complexes Supported by N,O-Donor Tripodal Ligands: Synthesis, Structure, and Ligand-Dependent Redox Behavior

Rosario Scopelliti, Marinella Mazzanti, Julie Renée Michelle Andrez

The preparation and characterization of a series of complexes of the Yb and Eu cations in the oxidation state II and III with the tetradentate N,O-donor tripodal ligands (tris(2-pyridylmethyl)amine (TPA), BPA(-) (HBPA=bis(2-pyridylmethyl)(2-hydroxybenzyl)a ...

2015

Subcomponent Self-Assembly of Rare-Earth Single-Molecule Magnets

A family of lanthanide complexes has been synthesized by the subcomponent self-assembly methodology. Molecular architectures, which were stable in solution and under ambient conditions, were designed by the in situ formation of ligands around lanthanide io ...

Amer Chemical Soc2013

Efficient and Rapid Synthesis of Chlorido-Bridged Half-Sandwich Complexes of Ruthenium, Rhodium, and Iridium by Microwave Heating

Rosario Scopelliti, Kay Severin, Zacharias Immanuel Grote, Julie Risse, Justus Tönnemann

The dinuclear complexes [(p-cymene)RuCl2]2 and [(cyclopentadienyl)MCl2]2 (M = Ru, Rh, Ir) are important starting materials in organometallic chemistry. The standard synthesis of these complexes involves heating of an alcoholic solution of RuIII, RhIII, or ...

Wiley-Blackwell2013

Energy transfer in coumarin-sensitised lanthanide luminescence: investigation of the nature of the sensitiser and its distance to the lanthanide ion

Anne-Sophie Chauvin, Julien Alexandre Andres

A series of lanthanide complexes Ln(dpxCy)(3) have been synthesised. The ligands are composed of a coordinating dipicolinic acid backbone decorated with a polyoxyethylene arm fitted with a coumarin moiety at its extremity. The nature of the coumarin ...

Royal Society of Chemistry2013

New Bisaqua Picolinate-Based Gadolinium Complexes as MRI Contrast Agents with Substantial High-Field Relaxivities

Lothar Helm, Marinella Mazzanti

Two new tripodal heptadentate ligands, H4dpaba (N,N'-bis[(6-carboxypyridin-2-yl)methyl]aspartic acid) and H3mpatcn(1,4-bis(methoxycarbonyl)-7-[(6-carboxypyridin-2-yl)methyl]-1,4,7-triazacyclononane), which bear one or two picolinate pendant arms, have been ...

Wiley-Blackwell2012

From Luminescent Lanthanide Complexes to Color Reproduction and Optical Document Security with Invisible Luminescent Inks

Julien Alexandre Andres

The present thesis deals with luminescent compounds based on lanthanide complexes that are suitable for color reproduction and optical document security with invisible luminescent inks. This thesis is divided in two distinct fields: chemistry, which produc ...

EPFL2012

Isoquinoline-Based Lanthanide Complexes: Bright NIR Optical Probes and Efficient MRI Agents

Lothar Helm, Eva Jakab Toth, Sandrine Villette

In the objective of developing ligands that simultaneously satisfy the requirements for MRI contrast agents and near-IR emitting optical probes that are suitable for imaging, three isoquinoline-based polyaminocarboxylate ligands, L1, L2 and L3, have been s ...

2012

Synthesis and Photophysical Properties of Ln(III)-DOTA-Bipy Complexes and Ln(III)-DOTA-Bipy-Ru-II Coordination Conjugates

Jean-Claude Bünzli, Svetlana Eliseeva

The synthesis and the systematic and comparative photo-physical study of a series of visible (Eu-III, Tb-III) and NIR-emitting (Nd-III, Yb-III) lanthanide complexes (Ln(2)L) and ruthenium lanthanide coordination conjugates (Ln(2)LRu) are reported. The Gd-I ...

Wiley-Blackwell2010

Sensitized near-IR luminescence of lanthanide complexes based on push-pull diketone derivatives

Jean-Claude Bünzli, Anne-Sophie Chauvin, Frédéric Gumy, Annina Aebischer

Lanthanide complexes with two push-pull diketone derivatives as sensitizers have been developed as synthons for near-infrared emitting materials. The ligand substituents consist of a carbazole moiety with hole-transport properties and an aromatic or hetero ...

2010

Multiphoton-Excited Luminescent Lanthanide Bioprobes: Two- and Three-Photon Cross Sections of Dipicolinate Derivatives and Binuclear Helicates

Jean-Claude Bünzli, Majed Chergui, Anne-Sophie Chauvin, Svetlana Eliseeva, Frank van Mourik, Bo Song, Andrea Cannizzo, Gerald Auböck

Multiphoton excited luminescent properties of water-soluble EuIII and TbIII complexes with derivatives of dipicolinic acid functionalized with a polyoxyethylene pendant arm and terminal groups, [Eu(LOMe)3]3-, [Eu(LNH2)3]3-, and [Tb(LOH)3]3-, as well as of ...

2010

Lanthanide chelates of (bis)-hydroxymethyl-substituted DTTA with potential application as contrast agents in magnetic resonance imaging

Lothar Helm

A novel bis-hydroxymethyl-substituted DTTA chelator N¢-Bz-C4,4¢-(CH2OH)2-DTTA (1) and its DTPA analogue C4,4¢-(CH2OH)2-DTPA (2) were synthesized and characterized. A variable-temperature 1H NMR spectroscopy study of the solution dynamics of their diamagnet ...

2009

Intrinsic quantum yields and radiative lifetimes of lanthanide tris(dipicolinates)

Jean-Claude Bünzli, Frédéric Gumy, Annina Aebischer

The efficiency with which the surroundings of trivalent lanthanide ions sensitize their luminescence (Zsens) is a key parameter in the design of highly emitting molecular edifices and materials. Evaluation of Zsens requires the measurement of the overall a ...

2009

Synthesis, structures and characterisations of truly homoleptic acetonitrile Ln3+ complexes in solid state and in solution

Rosario Scopelliti, Lothar Helm, Ines Raabe, Gabriella Eva Bodizs

Total halide abstraction from LnCl3 by Ag[Al(OC(CF3)3)4]/CH3CN has been confirmed for a series of lanthanide metal ions by the structural characterization of [Ln(CH3CN)n][Al(OC(CF3)3)4]3 (n = 9, Ln3+ = Nd, Eu, Gd, Dy; n = 8, Ln3+ = Tm) complexes. Evidence ...

2009

Modulating the Near-Infrared Luminescence of Neodymium and Ytterbium Complexes with Tridentate Ligands Based on Benzoxazole-Substituted 8-Hydroxyquinolines

Rosario Scopelliti, Jean-Claude Bünzli, Frédéric Gumy

An improved synthesis of 2-(2′-benzothiazole)- and 2-(2′-benzoxazole)-8-hydroxyquinoline ligands that combine a tridentate N,N,O-chelating unit for metal binding and extended chromophore for light harvesting is developed. The 2-(2′-benzoxazole)-8-hydroxyqu ...

2009