Multifunctional Dy Complexes with Triphenylmethanolates: Structural Diversity, Luminescence, and Magnetic Relaxation.

The coordination environment of magneto-luminescent Dy-based Single-Molecule Magnets (SMM) is a crucial factor influencing both magnetic and luminescent properties. In this work, we explore how triphenylmethanolate (PhCO), in combination with other ligands, can modulate the structure and, therefore, the magnetic properties of Dy-based SMM. Using triphenylmethanolate in combination with THF and pyridine (Py) as co-ligands, we synthesized a series of mononuclear -[Dy(OCPh)(THF)][BPh]·(2,6-MeCHN) (), -Dy(OCPh)(THF) (), -Dy(OCPh)(py) () and dinuclear [(PhCO)Dy(THF){(μ-Cl)Li(THF)}μ-Cl] () complexes where the Dy ion presents five- or six-coordinate geometries.

Designing a molecularly imprinted polymer-based electrochemical sensor for the sensitive and selective detection of the antimalarial chloroquine phosphate.

For the first time an electrochemical sensor based on nanomaterial-supported molecularly imprinted polymers (MIPs) is applied to the sensitive and specific determination of chloroquine phosphate (CHL). The sensor was produced using an electropolymerization (EP) approach, and it was formed on a glassy carbon electrode (GCE) using CHL as a template and 2-acrylamido-2-methyl-1-propane sulfonic acid (AMPS) and aniline (ANI) as functional monomers. Incorporating Prussian blue polyethyleneglycol-amine nanoparticles (PB@PEG-NH) in the MIP-based electrochemical sensor increased the active surface area and porosity.

Advanced Porous Nanomaterials: Synthesis, Properties, and Applications.

Porous nanomaterials have emerged as one of the most versatile and valuable classes of materials, captivating the attention of both scientists and engineers due to their exceptional functional and structural properties [...

Magnetic Iron Oxide Nanoparticles Coated by Coumarin-Bound Copolymer for Enhanced Magneto- and Photothermal Heating and Luminescent Thermometry.

In this work, we report on the synthesis and investigation of new hybrid multifunctional iron oxide nanoparticles (IONPs) coated by coumarin-bound copolymer, which combine magneto- or photothermal heating with luminescent thermometry. A series of amphiphilic block copolymers, including Coum-C-PPhOx-PMOx and Coum-C-PButOx-PMOx bearing luminescent and photodimerizable coumarin moiety, as well as coumarin-free PPhOx-PMOx, were evaluated for their utility as luminescent thermometers and for encapsulating spherical 26 nm IONPs. The obtained IONP@Coum-C-PPhOx-PMOx nano-objects are perfectly dispersible in water and able to provide macroscopic heating remotely triggered by an alternating current magnetic field (AMF) with a specific absorption rate (SAR) value of 240 W.

Luminescent Ln-based silsesquioxanes with a β-diketonate antenna ligand: toward the design of efficient temperature sensors.

We report the synthesis and single-crystal X-ray diffraction, magnetic, and luminescence measurements of a novel family of luminescent cage-like tetranuclear silsesquioxanes (PhSiO)(LnO)(O)(CHO)(EtOH)(CHCN)⋅2CHCN (where Ln = Tb, ; Tb/Eu, ; and Gd, ), featuring seven-coordinated lanthanide ions arranged in a one-capped trigonal prism geometry. Compounds and exhibit characteristic Tb and Tb/Eu-related emissions, respectively, sensitized by the chelating antenna acetylacetonate (acac) ligands upon excitation in the UV and visible spectral regions. Compound is used to assess the energies of the triplet states of the ligand.

Luminescent Er based single molecule magnets with fluorinated alkoxide or aryloxide ligands.

We report the synthesis, structures, and magnetic and luminescence properties of a series of new mono- and dinuclear Er complexes derived from sterically demanding aryloxide and fluorinated alkoxide ligands: [4-Bu-2,6-(PhCH)CHO]Er(THF) (1), [(CF)CO]Er(MeSiOH) (2), [(CF)CO]Er[(MeSi)NH] (3), [(CF)CO]Er(CHCH) (4), [(CF)CO]Er(-MeNCHCH) (5) and {[Ph(CF)CO]Er(μ-OC(CF)Ph)} (6). In compounds 1, 2, and 4, the Er ion is four-coordinated and adopts a distorted trigonal pyramidal geometry, while in 3, 5, and 6, the coordination geometry of Er is impacted by the presence of several relatively short Er⋯F distances, making them rather 6-coordinated. All compounds behave as field-induced Single Molecule Magnets (SMMs) and exhibit an Er characteristic near infrared (NIR) emission associated with the I → I transition with a remarkably long lifetime going up to 73 μs, which makes them multifunctional luminescent SMMs.

Tetranuclear lanthanide-based silsesquioxanes: towards a combination of a slow relaxation of the magnetization and a luminescent thermometry.

Lanthanide-based silsesquioxanes constitute an emerging family of cage-like metallasilsesquioxanes with exciting optical and magnetic properties. We report here the synthesis, structures and luminescence properties of a series of tetranuclear lanthanide-silsesquioxane compounds of general formula [NEt][(PhSiO)(Ln/Ln')(NO)(EtOH)(MeCN)]·4(MeCN) with different lanthanide ions (where Ln/Ln' = Dy/Eu (1), Dy/Tb (2) and Eu/Tb/Y (3)) and investigate the impact of the lanthanide ions combination on magnetic and photo-luminescent properties. Compound 1 behaves as a field-induced Single Molecule Magnet (SMM) and presents temperature-dependent luminescence characteristics of Eu making it an emissive thermometer working in the temperature range 293-373 K with the maximum relative sensitivity of 1.

Hybrid multifunctionalized mesostructured stellate silica nanoparticles loaded with β-diketonate Tb/Eu complexes as efficient ratiometric emissive thermometers working in water.

Despite the great effort made in recent years on lanthanide-based ratiometric luminescent nanothermometers able to provide temperature measurements in water, their design remains challenging. We report on the synthesis and properties of efficient ratiometric nanothermometers that are based on mesoporous stellate nanoparticles (MSN) of . 90 nm functionalized with an acetylacetonate (acac) derivative inside the pores and loaded with β-diketonate-Tb/Eu complexes able to work in water, in PBS or in cells.

Cascade strategy for triggered radical release by magnetic nanoparticles grafted with thermosensitive alkoxyamine.

The design of smart nanoplatforms presenting well-definite structures able to achieve controlled cascade action remotely triggered by external stimuli presents a great challenge. We report here a new nanosystem consisting of magnetic iron oxide nanoparticles covalently grafted with a thermosensitive radical initiator alkoxyamine, able to provide controlled and localized release of free radicals triggered by an alternating current (ac) magnetic field. These nanoparticles exhibit a high intrinsic loss power of 4.

Magneto-Induced Hyperthermia and Temperature Detection in Single Iron Oxide Core-Silica/Tb/Eu(Acac) Shell Nano-Objects.

Multifunctional nano-objects containing a magnetic heater and a temperature emissive sensor in the same nanoparticle have recently emerged as promising tools towards personalized nanomedicine permitting hyperthermia-assisted treatment under local temperature control. However, a fine control of nano-systems' morphology permitting the synthesis of a single magnetic core with controlled position of the sensor presents a main challenge. We report here the design of new iron oxide core-silica shell nano-objects containing luminescent Tb/Eu-(acetylacetonate) moieties covalently anchored to the silica surface, which act as a promising heater/thermometer system.

Temperature sensing in Tb/Eu-based tetranuclear silsesquioxane cages with tunable emission.

New luminescent cage-like tetranuclear silsesquioxanes [NEt][(PhSiO)(TbEu)(NO)(OH)(EtOH)(HO)]·4(EtOH) (1) and [NEt][(PhSiO)(TbEu)(NO)(EtOH)(MeCN)]·4(MeCN) (2) present a tunable thermosensitive Tb-to-Eu energy transfer driven by Tb and Eu emission and may be used as temperature sensors operating in the range 41-100 °C with excellent linearity ( = 0.9990) and repeatability (>95%). The thermometer performance was evidenced by the maximum relative sensitivity of 0.

Multifunctionalized Mesostructured Silica Nanoparticles Containing Mn2 Complex for Improved Catalase-Mimicking Activity in Water.

We report the synthesis of a hybrid nanocatalyst obtained through the immobilization of bio-inspired [{Mn(bpy)(HO)}(µ-2-MeCHCOO)(µ-O){Mn(bpy)(NO)}]NO compound into functionalized, monodispersed, mesoporous silica nanoparticles. The in situ dual functionalization sol-gel strategy adopted here leads to the synthesis of raspberry-shaped silica nanoparticles of ca. 72 nm with a large open porosity with preferential localization of 1,4-pyridine within the pores and sulfobetaine zwitterion on the nanoparticles' periphery.

Using N-Heterocyclic Carbenes as Weak Equatorial Ligands to Design Single-Molecule Magnets: Zero-Field Slow Relaxation in Two Octahedral Dysprosium(III) Complexes.

We report the synthesis, structures, and magnetic investigations of two new octahedral dysprosium complexes, based on the original N-heterocyclic carbene (NHC) tridentate bis(phenoxide) ligand, of the respective formulas -[DyL(THF)Cl] () and -[DyL(THF)][BPh] (), where L = 1,3-bis(3,5-di--butyl-2-oxidophenyl)-5,5-dimethyl-3,4,5,6-tetrahydropyrimidin-1-ium chloride and THF = tetrahydrofuran. The short Dy-O distances in the axial direction in association with the weak donor ability of the NHC moiety provide a suitable environment for slow relaxation of magnetization, overcoming the previous single-molecule magnets based on NHC ligands.

A rational study of the influence of Mn-insertion in Prussian blue nanoparticles on their photothermal properties.

We investigated a series of Mn-Prussian blue (PB) nanoparticles NaMnFe[Fe(CN)]·HO of similar size, surface state and cubic morphology with various amounts of Mn synthesized through a one step self-assembly reaction. We demonstrated by a combined experimental-theoretical approach that during the synthesis, Mn substituted Fe up to a Mn/Na-Mn-Fe ratio of 32 at% in the PB structure, while for higher amounts, the Mn[Fe(CN)] analogue is obtained. For comparison, the post-synthetic insertion of Mn2+ in PB nanoparticles was also investigated and completed with Monte-Carlo simulations to probe the plausible adsorption sites.

Long-term performances of polylactide/iron oxide nanoparticles core-shell fibrous nanocomposites as MRI-visible magneto-scaffolds.

There is a growing interest in magnetic nanocomposites in biomaterials science. In particular, nanocomposites that combine poly(lactide) (PLA) nanofibers and superparamagnetic iron oxide nanoparticles (SPIONs), which can be obtained by either electrospinning of a SPION suspension in PLA or by precipitating SPIONs at the surface of PLA, are well documented in the literature. However, these two classical processes yield nanocomposites with altered materials properties, and their long-term fate and performances have in most cases only been evaluated over short periods of time.

Assessing the combination of magnetic field stimulation, iron oxide nanoparticles, and aligned electrospun fibers for promoting neurite outgrowth from dorsal root ganglia in vitro.

Magnetic fiber composites combining superparamagnetic iron oxide nanoparticles (SPIONs) and electrospun fibers have shown promise in tissue engineering fields. Controlled grafting of SPIONs to the fibers post-electrospinning generates biocompatible magnetic composites without altering desired fiber morphology. Here, for the first time, we assess the potential of SPION-grafted scaffolds combined with magnetic fields to promote neurite outgrowth by providing contact guidance from the aligned fibers and mechanical stimulation from the SPIONs in the magnetic field.

High magnetization reversal barriers in luminescent dysprosium octahedral and pentagonal bipyramidal single-molecule magnets based on fluorinated alkoxide ligands.

We report the synthesis and structures of three luminescent dysprosium(iii) complexes based on fluorinated alkoxide ligands of formulas [Dy(L1)2(THF)4][BPh4]·0.5THF (1), [Dy(L2)2(THF)5][BPh4]·2.5THF (2) and [Dy(L3)2(THF)5][BPh4]·2THF (3) (L1 = (CF3)3CO-, L2 = C6F5C6F4O-, L3 = C6F5C(CH3)O-).

New Luminescent Tetranuclear Lanthanide-Based Silsesquioxane Cage-Like Architectures.

Invited for the cover of this issue are Alexey N. Bilyachenko, Joulia Larionova and co-workers at the Russian Academy of Sciences, the Peoples' Friendship University of Russia, and University of Montpellier. The image depicts lanthanide-based cage-like silsesquioxanes exhibiting magnetic and luminescence properties that could constitute a particularly interesting new family related to multifunctional nanomaterials.

Single-molecule magnet behavior in heterolopetic Dy-chloro-diazabutadiene complexes: influence of the nuclearity and ligand redox state.

We report the synthesis, structure and magnetic properties investigations of a series of new dysprosium heteroleptic mono- and dinuclear complexes based on the association of chloride and different diazabutadiene (DAD2R = [2,6-iPr2C6H3N-CR[double bond, length as m-dash]CR-NC6H3iPr2-2,6]; R = H, Me) ligands showing different redox states. While using dianionic DAD2R ligands affords the formation of dichloro-bridged dinuclear complexes [Dy2(DAD2R)(μ-Cl)2(THF)2] (R = H (1), Me (2)), two different mononuclear complexes of general formula [DyCl2(DAD2R)(THF)2] (R = H (3), Me (4)) could be obtained with either a radical monoanionic and a monoanionic DAD2R state, respectively. Remarkably, all the complexes exhibit a slow relaxation of their magnetization where the relaxation dynamics depends on both the nuclearity of the system and the DAD2R redox state.

New Luminescent Tetranuclear Lanthanide-Based Silsesquioxane Cage-Like Architectures.

The synthesis, structure, magnetic, and luminescence properties investigations of four new cage-like lanthanide-based silsesquioxanes (Cat) [(PhSiO ) (LnO ) (O)(NO ) (EtOH) (MeCN) ] (where Cat =Et N , PPh P and Ln =Eu , Tb and (Ph P) [(PhSiO ) (TbO ) (O) (NO ) ]⋅10MeCN are reported. They present an unusual prism-like topology of cage architectures and lanthanide-characteristic emission, which makes them the first luminescent cage-like lanthanide silsesquioxanes. One of the Tb -based cages presents a magnetic spin-flip transition.

Synthesis, Structure, Magnetic and Photoluminescent Properties of Dysprosium(III) Schiff Base Single-Molecule Magnets: Investigation of the Relaxation of the Magnetization.

We report here the synthesis, structure, magnetic and photoluminescent properties of three new bifunctional Schiff-base complexes [Dy(L ) (py) ][B(Ph) ]⋅py (1), [Dy(L ) Cl(DME)] ⋅ 0.5DME (2) and [Dy(L ) Cl] ⋅ 2.5(C H ) (3) (HL =Phenol, 2,4-bis(1,1-dimethylethyl)-6-[[(2-methoxy-5-methylphenyl)imino]methyl]; HL =Phenol, 2,4-bis(1,1-dimethylethyl)-6-[[(2-methoxyphenyl)imino]methyl]).

Single-molecule magnet behavior in luminescent carbazolyl Dy(iii) octahedral complexes with a quasi linear N-Dy-N angle.

We report the synthesis, photoluminescence and magnetic properties of two octahedral dysprosium complexes [DyR2(py)4][BPh4]·2py (1) and [DyR2(THF)4][BPh4] (2) (R = carbazolyl, py = pyridine, THF = tetrahydrofuran) exhibiting a quasi linear N-Dy-N angle in the axial direction, suitable for providing a coordination environment allowing the zero-field slow relaxation of magnetization.

Fashioning Prussian Blue Nanoparticles by Adsorption of Luminophores: Synthesis, Properties, and Imaging.

We report the postsynthetic functionalization of Prussian blue (PB) nanoparticles by two different luminophores (2-aminoanthracene and rhodamine B). We show that the photoluminescence properties of the fluorophores are modified by a confinement effect upon adsorption and demonstrate that such multifunctional nanosized systems could be used for in vitro imaging.

Room temperature magnetoelectric coupling in a molecular ferroelectric ytterbium(III) complex.

Magnetoelectric (ME) materials combine magnetic and electric polarizabilities in the same phase, offering a basis for developing high-density data storage and spintronic or low-consumption devices owing to the possibility of triggering one property with the other. Such applications require strong interaction between the constitutive properties, a criterion that is rarely met in classical inorganic ME materials at room temperature. We provide evidence of a strong ME coupling in a paramagnetic ferroelectric lanthanide coordination complex with magnetostrictive phenomenon.