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)(H2O)6]∞ for the lightest lanthanide ions (Ln = La-Dy except Pm), while it is [Ln(tma)(H2O)5·3.5H2O]∞ for the heaviest ones (Ho-Lu plus Y). For the heaviest lanthanide ions, reactions at 50 °C lead to a third structural family with the general chemical formula [Ln(tma)(H2O)3·1.5H2O]∞ with Ln = Ho-Lu plus Y. Homo-lanthanide coordination polymers that belong to the latter two families do not exhibit luminescence in the visible region. Therefore, we used a phase induction strategy to obtain molecular alloys that belong to these structural families and show sizeable emission. The random distribution of the lanthanide ions over the metallic sites has been investigated using 89Y and 139La solid-state NMR spectroscopy experiments. Luminescent properties of homo- and hetero-nuclear coordination polymers based on Eu3+ and Tb3+ have been studied in detail and compared. As a result, this study strongly suggests that exchange-based intermetallic energy transfer mechanisms play an important role in these systems. It also suggests the presence of an intermetallic exchange pathway through π-stacking interactions.

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. Therefore, a brightness calculation or a luminance measurement are mandatory for a quantitative estimation of the luminescence intensity. The calculated brightness appears to be a convenient quantitative parameter for the estimation of the luminescence intensity in the infrared domain, in which luminance is senseless. It is also a useful parameter in the visible domain, but one must keep in mind that only compounds with similar colorimetric coordinates can be compared. For comparing the luminescence intensities of compounds that exhibit different emission colors, the luminance measurement seems to be the most efficient method. A home-made setup that allows this measurement with high reproducibility is described in detail. The luminance of several lanthanide-based coordination polymers with benzene-poly-carboxylate ligands is measured, and the results are compared with brightness and quantum yield measurements. A standard is suggested for calibration.

Expanding the Toolbox of Octahedral Molybdenum Clusters and Nanocomposites Made Thereof: Evidence of Two-Photon Absorption Induced NIR Emission and Singlet Oxygen Production.

Bright NIR phosphorescence from octahedral molybdenum clusters has been known since the 1980s. However, their behavior toward NIR excitation has never been investigated. Here we report their abilities to emit NIR light and produce singlet oxygen upon two-photon absorption. This behavior is observed in solution, in the solid state, and when clusters are embedded homogeneously in a poly(dimethylsiloxane) matrix. Such discoveries open new perspectives in several fields like optoelectronics, photodynamic therapy, or bioimaging.

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

Isostructural lanthanide-based coordination polymers with general chemical formula [Ln(phen)(glu)(NO3)]∞ with Ln = La-Tm (except Ce and Pm) have been synthesized by hydrothermal methods (H2glu stands for glutaric acid and phen stands for 1,10-phenantroline). They crystallize in the monoclinic system with the P21/c (no. 14) space group. The crystal structure has been solved on the basis of the La derivative. It can be described as the superimposition of molecular chains of dimeric La(phen)(NO3)-La(phen)(NO3) units bridged by glutarate ligands. Luminescent properties have been explored and show that the Eu derivative exhibits the highest luminance observed for Eu-based coordination polymers (85 to 105 cd·m-2). Effects of the dilution of the Eu3+ and Tb3+ luminescent ions by Gd3+ optically inactive ions are unexpected and to the best of our knowledge unprecedented. This could be related to the different intermetallic energy-transfer mechanisms in competition and to the nonisotropic distribution of the lanthanide ions in these molecular alloys. The investigation of molecular alloys with general chemical formula [Eu1-xTbx(phen)(glu)(NO3)]∞ with 0 ≤ x ≤ 1 highlights a very sizable and constant Eu3+ luminescence whatever the x value, which further confirms the existence of very strong intermetallic energy transfers in this family of compounds. It is also noticeable that some coordination polymers based on weakly emissive lanthanide ions exhibit very well defined emission spectra.

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 [Ln2(dcpa)3(H2O)]∞ 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 (H2dcpa). They present particularly high thermal stability for coordination compounds (up to 400 °C). Their luminescent properties have been studied in detail. Interestingly an insensitivity to water coordination as well as a very strong effect of optical dilution is observed. Therefore, molecular alloys with very high lanthanum concentration have been prepared. Some of them present highly tunable and very intense luminescence. For example, to the best of our knowledge, [Sm0.04La1.96(dcpa)3(H2O)]∞ presents one of the highest overall quantum yields measured so far for a Sm3+-based coordination compound (QSmLigand = 9.2%), and [Nd0.03Sm0.14Eu0.03La1.8(dcpa)3(H2O)]∞ is one of the brightest (12 Cd·m-2 under 0.75 mW·cm-2 UV flux) multiemissive visible and near-infrared lanthanide-coordination polymers reported to date.

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 (dcpa2-) lead to two families of isostructural coordination polymers: family F1 that gathers compounds with the general chemical formula [Ln2(dcpa)3(H2O)]∞ with Ln = La-Gd (except Pm) and family F2 that gathers compounds with general chemical formula [Ln2(dcpa)3(H2O)5·3H2O]∞ with Ln = Tb-Lu plus Y. Heterolanthanide molecular alloys that contain both Eu3+ and Tb3+ ions have been prepared in both structural families. Their luminescence properties have been studied, especially from the brightness point of view. This study revealed that structural family F1 provides molecular alloys that are much more luminescent than those of structural family F2. Therefore, a phase-induction strategy was followed that allowed the design of some molecular alloys (La/Tb/Eu and La/Dy) that are, to the best of our knowledge, among the most luminescent coordination polymers reported so far. This study opens the way to bright luminescent bar codes as well as to bright white luminescent lanthanide-based coordination polymers.

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 (mip2-) have the general chemical formula [Ln2(mip)3(H2O)8·4H2O]∞ with Ln = Nd-Er except Pm plus Y (symbolized by [Ln2(mip)3]∞). 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. A molecular alloy that involved six different lanthanide ions (Nd3+, Sm3+, Eu3+, Gd3+, Tb3+, Dy3+) has been prepared and its luminescent properties have been studied. This compound, under a unique irradiation wavelength (λexc = 325 nm), exhibits almost 20 emission peaks in both the visible and the NIR regions at room temperature. This unprecedented richness of the emission spectrum could be of great interest as far as luminescent bar-codes are targeted.

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)3(H2O)2]∞ for Ln = La or Ce and [Ln(cpbOH)(H2O)2·(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.

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 DyIII 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. Overall, the material shows a magnetic slow relaxation in absence of external static field and a hysteretic behavior at 0.5 K. Low-temperature magnetic studies, diamagnetic doping, and ab initio calculations highlight the crucial role played by the Dy-Dy ferromagnetic interaction. Overall, we report an original magnetic object at the frontier between single-chain magnets and single-molecule magnets that host intrachain couplings that cancel quantum tunneling between the MBBs. This compound is evidence that a bottom-up approach through MOF design can induce spontaneous organization of MBBs able to produce remarkable molecular magnetic materials.

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 (dcpa2-) with the heaviest lanthanide ions lead to a family of compounds with the general chemical formula [Ln2(dcpa)3(H2O)5·3H2O]∞, 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. These compounds show potential interest as multiemissive materials (visible and infrared light between 450 and 1600 nm) and could find application as luminescent bar codes.

Brightness and Color Tuning in a Series of Lanthanide-Based Coordination Polymers with Benzene-1,2,4,5-tetracarboxylic Acid as a Ligand.

Reactions in water between the sodium salt of benzene-1,2,4,5-tetracarboxylic acid (H4btec) and lanthanide ions (Sm-Dy) led to a series of isostructural lanthanide-based coordination polymers with the general chemical formula [Ln4(btec)3(H2O)12·20H2O]∞ with Ln = Sm-Dy. The family has been structurally characterized. From a luminescent point of view, the heterodinuclear strategy has been successfully applied and allows significant brightness enhancement (+35%) and color tuning from green to yellow to orange to red.

Nanometrization of Lanthanide-Based Coordination Polymers.

Heteronuclear lanthanide-based coordination polymers are microcrystalline powders, the luminescence properties of which can be precisely tuned by judicious choice of the rare-earth ions. In this study, we demonstrate that such materials can also be obtained as stable solutions of nanoparticles in non-toxic polyols. Bulk powders of the formula [Ln2-2x Ln'2x (bdc)3 ⋅4 H2 O]∞ (where H2 bdc denotes 1,4-benzene-dicarboxylic acid, 0≤x≤1, and Ln and Ln' denote lanthanide ions of the series La to Tm plus Y) afford nanoparticles that have been characterized by dynamic light-scattering (DLS) and transmission electron microscopy (TEM) measurements. Their luminescence properties are similar to those of the bulk materials. Stabilities versus time and versus dilution with another solvent have been studied. This study has revealed that it is possible to tune the size of the nanoparticles. This process offers a reliable means of synthesizing suspensions of nanoparticles with tunable luminescence properties and tunable size distributions in a green solvent (glycerol). The process is also extendable to other coordination polymers and other solvents (ethylene glycol, for example). It constitutes a new route for the facile solubilization of lanthanide-based coordination polymers.

A family of lanthanide-based coordination polymers with boronic Acid as ligand.

Reactions in water between the sodium salt of 4-carboxyphenylboronic acid (Hcpb) and lanthanide ions (Pr-Nd, Sm-Lu, and Y) led to a family of lanthanide-based coordination polymers with general chemical formula {[Ln(cpbOH)(H2O)2](cpb)}∞. Structural characterizations were ensured by single-crystal X-ray diffraction and solid-state NMR spectroscopy ((11)B, (13)C, and (89)Y). This family of compounds constitutes the first example of lanthanide-based coordination polymers involving 4-carboxyphenylboronic acid as ligand. To evaluate their potential usefulness, luminescent and magnetic properties of some of the compounds that constitute this family were explored. From a magnetic point of view, the Yb(III) compound is the more promising. On the other hand, upon UV irradiation (λexc = 303 nm) ligand phosphorescence is quite intense and offers a sizable blue component to emission spectra. This is quite unusual and can constitute an asset as far as white emission is targeted. Moreover, luminescence properties of these compounds are highly temperature-dependent, and some of them seem promising as molecular thermometers.

Influence of photoinduced electron transfer on lanthanide-based coordination polymer luminescence: a comparison between two pseudoisoreticular molecular networks.

The luminescent properties of two families of heteronuclear lanthanide-containing coordination polymers are compared. These families have general chemical formulas [Ln2-2xLn'2x(ip)3(H2O)9·6H2O]∞ and [Ln2-2xLn'2x(aip)2(H2O)10·(aip)·4H2O]∞ where H2ip and H2aip stand for isophthalic acid and 5-amino-isophthalic acid, respectively, and where Ln and Ln' are one of the lanthanide ions between Sm(3+) and Dy(3+). Heteronuclear compounds that belong to each family are isostructural to the already reported homonuclear compounds [Gd2(ip)3(H2O)9·6H2O]∞ and [Eu2(aip)2(H2O)10·(aip)·4H2O]∞, respectively. These two crystal structures are very similar. However, despite similar chemical formulas, similar crystal structures, and similar hydration rates, these two families of compounds present very different luminescent properties that have thus been deeply investigated. This study demonstrates that these different optical behaviors can be attributed to the presence of a PET (photoinduced electron transfer) mechanism that is only present in the amino-isophthalate-containing coordination polymers.