Halogen-Bonds-Based Strategy for the Design of Highly Luminescent Lanthanide Coordination Polymers as Taggants for Plastic Waste Sorting.

Reactions in water between a lanthanide ion and 3,4,5,6-tetrachloro-phthalate lead to a new series of iso-structural coordination polymers with general chemical formula [Ln(tcpa)(HO)] with Ln = Eu-Yb plus Y. The crystal structure has been solved on the Y-derivative. This compound crystallizes in the monoclinic system, space group 2/ (no.

Lanthanide-Based Coordination Polymers Molecular Alloys Stability: A Thermochemical Approach.

In this study, we investigate the thermodynamics of lanthanide-based coordination polymer molecular alloys. We demonstrate that if lanthanide ions have many chemical similarities, the solubility of homo-lanthanide-based coordination polymers can vary significantly from one lanthanide ion to another. Indeed, we experimentally determine the solubility constants of a series of isostructural homo-lanthanide coordination polymers, with general chemical formula [Ln(bdc)(HO)] with Ln = La-Er plus Y and where bdc symbolizes 1,4-benzene-di-carboxylate.

Metallogels: a novel approach for the nanostructuration of single-chain magnets.

In this study we demonstrate that single-chain magnets (SCMs) can be assembled in gel phase and transferred intact on surface. We take advantage of a family of SCMs based on Tb ions and nitronyl-nitroxides radicals functionalized with short alkyl chains known to form crystalline supramolecular nanotubes interacting with heptane acting as crystallizing solvent. When the radicals are functionalized with long aliphatic chains a robust gel is formed with similar structural and functional properties respect to its crystalline parent.

Luminance and Brightness: Application to Lanthanide-Based Coordination Polymers.

Measuring the luminance of lanthanide-based coordination polymers under UV excitation is of prime importance for many technological applications. This study highlights that the quantum yield gives no information about the luminescence intensity of a solid-state compound. Indeed, compounds with high quantum yield can actually be poorly luminescent.

Investigation of Intermetallic Energy Transfers in Lanthanide Coordination Polymers Molecular Alloys: Case Study of Trimesate-Based Compounds.

Reactions in water at ambient temperature and pressure between a lanthanide ion and benzene-1,3,5-tricarboxylate (or trimesate) lead to two series of iso-structural coordination polymers. Their general chemical formula is [Ln(tma)(HO)] for the lightest lanthanide ions (Ln = La-Dy except ), while it is [Ln(tma)(HO)·3.5HO] for the heaviest ones (Ho-Lu plus Y).

Synthesis, Crystal Structure, and Luminescence Properties of the Iso-Reticular Series of Lanthanide Coordination Polymers Synthesized from Hexa-Lanthanide Molecular Precursors.

Microwave-assisted reactions in DMSO, between a hexa-lanthanide octahedral complex ([Ln(μ-O)(μ-OH)(NO)(HO)·2NO·2HO] with Ln = Nd-Yb plus Y) and either 3-halogenobenzoic acid (hereafter symbolized by 3-bH with = f or c for fluoro or chloro, respectively) or 4-halogenobenzoic acid (hereafter symbolized by 4-bH with = f, c, or b for fluoro, chloro, or bromo, respectively), lead to 1D lanthanide coordination polymers. These coordination polymers are almost iso-reticular. The crystal structure is described on the basis of the coordination polymer with chemical formula [Tb(4-fb)(DMSO)(HO)·DMSO] obtained from 4-fluorobenzoic acid (4-fbH) and the Tb-based octahedral complex: It crystallizes in the triclinic system, space group 1̅ (n°2), with the following cell parameters: = 9.

Hexanuclear Molecular Precursors as Tools to Design Luminescent Coordination Polymers with Lanthanide Segregation.

Solvothermal reactions between hexanuclear complexes with the general chemical formula [Ln(μ-O)(μ-OH)(NO)(HO)]·2NO·2HO and 2-bromobenzoic acid (2-bbH) lead to a series of isostructural one-dimensional coordination polymers with the general chemical formula [Ln(2-bb)] with Ln = Sm, Eu, Tb, Dy, and Y. These coordination polymers crystallize in the orthorhombic space group 2 (No. 43) with the following cell parameters: = 29.

Single-chain magnet behavior in a finite linear hexanuclear molecule.

The careful monitoring of crystallization conditions of a mixture made of a Tb building block and a substituted nitronyl-nitroxide that typically provides infinite coordination polymers (), affords a remarkably stable linear hexanuclear molecule made of six Tb ions and five NIT radicals. The are double-bridged by water molecules but calculations demonstrate that this bridge is inefficient in mediating any magnetic interaction other than a small dipolar antiferromagnetic coupling. Surprisingly the , despite being finite molecules, show a single-chain magnet (SCM) behavior.

Highly Luminescent Europium-Based Heteroleptic Coordination Polymers with Phenantroline and Glutarate Ligands.

Isostructural lanthanide-based coordination polymers with general chemical formula [Ln(phen)(glu)(NO)] with Ln = La-Tm (except Ce and Pm) have been synthesized by hydrothermal methods (Hglu stands for glutaric acid and phen stands for 1,10-phenantroline). They crystallize in the monoclinic system with the 2/ (no. 14) space group.

A Journey in Lanthanide Coordination Chemistry: From Evaporable Dimers to Magnetic Materials and Luminescent Devices.

ConspectusLanthanide ions are prime ingredients for the design of compounds, materials, and devices with unique magnetic and optical properties. Accordingly, coordination chemistry is one of the best tools for building molecular edifices from these ions because it allows careful control of the ions' environment and of the dimensionality of the final compound.In this Account, we review our results on lanthanide-based dimers.

High Luminance of Heterolanthanide-Based Molecular Alloys by Phase-Induction Strategy.

Reactions in water of lanthanide chlorides with the sodium salt of 4,5-dichlorophthalate (dcpa) lead to two families of isostructural coordination polymers: family that gathers compounds with the general chemical formula [Ln(dcpa)(HO)] with Ln = La-Gd (except Pm) and family that gathers compounds with general chemical formula [Ln(dcpa)(HO)·3HO] with Ln = Tb-Lu plus Y. Heterolanthanide molecular alloys that contain both Eu and Tb ions have been prepared in both structural families. Their luminescence properties have been studied, especially from the brightness point of view.

Rational Design of Dual IR and Visible Highly Luminescent Light-Lanthanides-Based Coordination Polymers.

A series of isostructural homo- and heterolanthanide coordination polymers of formula [Ln(dcpa)(HO)] with Ln = La-Gd have been obtained by reactions in water between the lightest lanthanide chlorides and the disodium salt of 4,5-dichlorophthalic acid (Hdcpa). They present particularly high thermal stability for coordination compounds (up to 400 °C). Their luminescent properties have been studied in detail.

Sonocrystallization as an Efficient Way to Control the Size, Morphology, and Purity of Coordination Compound Microcrystallites: Application to a Single-Chain Magnet.

The size, morphology, and purity control of coordination compound powders is a key stage for their conversion into materials and devices. In particular, surface science techniques require highly pure bulk materials with a narrow crystallite-size distribution together with straightforward, scalable, and reproducible crystallization procedures. In this work we demonstrate how sonocrystallization, i.

Self-assembly of a terbium(III) 1D coordination polymer on mica.

The terbium(III) ion is a particularly suitable candidate for the creation of surface-based magnetic and luminescent devices. In the present work, we report the epitaxial growth of needle-like objects composed of [Tb(hfac)·2HO] (where hfac = hexafluoroacetylacetonate) polymeric units on muscovite mica, which is observed by atomic force microscopy. The needle-like shape mimics the structure observed in the crystalline bulk material.

Hetero-hexalanthanide Complexes: A New Synthetic Strategy for Molecular Thermometric Probes.

Reactions in solvothermal or microwave-assisted conditions between a hexanuclear rare-earth entity ([Ln] with Ln = Eu-Dy) and -halogeno-benzoic acids lead to three series of isostructural complexes with respective chemical formulas [Ln(μ-OH)(HO)(NO)(3-cb)]·4CHCN, [Ln(μ-OH)(HO)(NO)(3-bb)]·6CHCN, and [Ln(μ-OH)(HO)(NO)(3-ib)]·6CHCN, where 3-cb, 3-bb, and 3-ib represent 3-chloro-, 3-bromo-, and 3-iodo-benzoate, respectively. These three series of compounds are almost isostructural. Their luminescent properties, in the solid and solution states, have been studied in detail and compared.

Chiral Supramolecular Nanotubes of Single-Chain Magnets.

We report a single-chain magnet (SCM) made of a terbium(III) building block and a nitronyl-nitroxide radical (NIT) functionalized with an aliphatic chain. This substitution is targeted to induce a long-range distortion of the polymeric chain and accordingly it gives rise to chains that are curled with almost 20 nm helical pitch. They self-organize as a chiral tubular superstructure made of 11 chains wound around each other.

A supramolecular chain of dimeric Dy single molecule magnets decorated with azobenzene ligands.

We report the synthesis, ab initio calculations, magnetic and optical characterization of a Dy-based dimeric compound named DyAZO. The dimers self-organize into a supramolecular chain decorated with photo-isomerizable azobenzene ligands. DyAZO displays single-molecule magnet (SMM) behavior.

Synthesis and crystal structure of a new coordination polymer based on lanthanum and 1,4-phenyl-enedi-acetate ligands.

Reaction in gel between the sodium salt of 1,4-phenyl-enedi-acetic acid (NaCOH-Na -pda) and lanthanum chloride yields single crystals of the three-dimensional coordination polymer poly[[tetra-aqua-tris-(μ-1,4-phenyl-enedi-acetato)-dilanthanum(III)] octa-hydrate], {[La(CHO)(HO)]·8HO}. The La coordination polyhedron can be described as a slightly distorted monocapped square anti-prism. One of the two -pda ligands is bound to four La ions and the other to two La ions.

Multi-Emissive Lanthanide-Based Coordination Polymers for Potential Application as Luminescent Bar-Codes.

Isostructural lanthanide-based coordination polymers that are obtained by reactions in water of a lanthanide chloride and the sodium salt of 5-methoxyisophthalate (mip) have the general chemical formula [Ln(mip)(HO)·4HO] with Ln = Nd-Er except Pm plus Y (symbolized by [Ln(mip)]). Some of these homo-lanthanide compounds present very high luminescence brightness. The weak intermetallic energy transfer between lanthanide ions observed in these compounds allows the design of hetero-lanthanide coordination polymers with tunable luminescence properties.

Microcrystalline Core-Shell Lanthanide-Based Coordination Polymers for Unprecedented Luminescent Properties.

Microcrystalline core-shell powders of lanthanide-based coordination polymers with general chemical formula ([Ln(cpbOH)])@([Ln'(cpbOH)]) with Hcpb = 1,4-carboxyphenylboronic acid have been synthesized and structurally characterized. Their luminescent properties have been studied. They are drastically different from those of heterolanthanide coordination polymers, also called "molecular alloys", that present the same crystal structure and chemical composition.

Lanthanide-Based Coordination Polymers With 1,4-Carboxyphenylboronic Ligand: Multiemissive Compounds for Multisensitive Luminescent Thermometric Probes.

Reactions in water of lanthanide chlorides with the sodium salt of 1,4-carboxyphenylboronic acid lead to two series of isostructural compounds with respective general chemical formulas [Ln(cpb)(HO)] for Ln = La or Ce and [Ln(cpbOH)(HO)·(cpb)] for Ln = Pr-Lu (except Pm) plus Y. Heterolanthanide coordination polymers that are isostructural to the second series have been synthesized, and their photophysical properties have been studied. This study evidences that it is possible to design multiemissive lanthanide-based coordination polymers that could find their application as multigauge luminescent thermometric probes.

Strong Magnetic Coupling and Single-Molecule-Magnet Behavior in Lanthanide-TEMPO Radical Chains.

The rational design of molecular chains made of 4f ions and substituted 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) radical is presented. The reaction of Ln(hfac)·2HO (hfac = hexafluoroacetylacetonate) and the 4-cyano-2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO-CN) radical affords air- and moisture-stable isostructural molecular chains of the formula [Ln(hfac)TEMPO-CN] for Ln = Gd and Tb, whereas zero-dimensional complexes of the formula [Dy(hfac)(TEMPO-CN)][Dy(hfac)(HO)] are obtained for Ln = Dy. To the best of our knowledge, the Gd derivative, Gd-TEMPO-CN, shows one of the strongest antiferromagnetic (AF) couplings for Gd-radical pairs ever reported with J/ k = -21.

Lanthanide-Based Coordination Polymers with a 4,5-Dichlorophthalate Ligand Exhibiting Highly Tunable Luminescence: Toward Luminescent Bar Codes.

Reactions in water of 4,5-dichlorophthalate (dcpa) with the heaviest lanthanide ions lead to a family of compounds with the general chemical formula [Ln(dcpa)(HO)·3HO], where Ln = Tb-Lu, Y. The synthesis, crystal structure, thermal behavior, and luminescent properties of this series of homonuclear compounds are described. Additionally, this family can be extended to isostructural heteronuclear compounds that can contain some light lanthanide ions and therefore present some original photophysical properties.

Magnetic Slow Relaxation in a Metal-Organic Framework Made of Chains of Ferromagnetically Coupled Single-Molecule Magnets.

We report the study of a Dy-based metal-organic framework (MOF) with unprecedented magnetic properties. The compound is made of nine-coordinated Dy magnetic building blocks (MBBs) with poor intrinsic single-molecule magnet behavior. However, the MOF architecture constrains the MBBs in a one-dimensional structure that induces a ferromagnetic coupling between them.

Hexalanthanide Complexes as Molecular Precursors: Synthesis, Crystal Structure, and Luminescent and Magnetic Properties.

Reaction of hexanuclear octahedral molecular precursors with a 3-chlorobenzoate ligand affords an unprecedented family of isostructural polylanthanide complexes via solvothermal and microwave-assisted syntheses in an acetonitrile medium. The general chemical formula of the compounds that constitute this series is {[Ln(μ-OH)(HO)(NO)(3-cb)]·(CHCN)}, where 3-cb stands for 3-chlorobenzoate and Ln = Eu, Tb, Dy, Ho, Er, or Y. The crystal structure, solubility, and magnetic and luminescent properties of these complexes have been studied.