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)2 [(PhSiO1.5 )8 (LnO1.5 )4 (O)(NO2.5 )6 (EtOH)2 (MeCN)2 ] (where Cat+ =Et4 N+ , PPh4 P+ and Ln3+ =Eu3+ , Tb3+ and (Ph4 P)4 [(PhSiO1.5 )8 (TbO1.5 )4 (O)2 (NO2.5 )8 ]⋅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 Tb3+ -based cages presents a magnetic spin-flip transition.

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. Read the full text of the article at 10.1002/chem.202003351.

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

Dysprosium Single-Molecule Magnets with Bulky Schiff Base Ligands: Modification of the Slow Relaxation of the Magnetization by Substituent Change.

The synthesis, and magnetic and photoluminescence investigations of two bifunctional dysprosium complexes based on tridentate Schiff base ligands is reported. Magnetic investigations reveal a genuine single-molecule magnet (SMM) behavior, with out-of-phase signals up to 60 K, and tunable emission arising from the Schiff base ligands.

Prussian Blue Analogues for the Separation of Hydrocarbons in Humid Conditions.

The relative affinity of a series of Prussian Blue analogues presenting various chemical compositions for the adsorption of different gases, such as water vapor and hydrocarbons, was studied. The ability of Co[CoIII(CN)6]0.66·5.2H2O for the separation of hydrocarbons in a humid atmosphere was demonstrated.

Novel Catalyst Composites of Ni- and Co-Based Nanoparticles Supported on Inorganic Oxides for Fatty Acid Hydrogenations.

In the quest to develop nanometrically defined catalytic systems for applications in the catalytic valorization of agri-food wastes, small Ni-based nanoparticles supported on inorganic solid supports have been prepared by decomposition of organometallic precursors in refluxing ethanol under H2 atmosphere, in the presence of supports exhibiting insulating or semi-conductor properties, such as MgAl2O4 and TiO2, respectively. The efficiency of the as-prepared Ni-based nanocomposites has been evaluated towards the hydrogenation of unsaturated fatty acids under solvent-free conditions, with high selectivity regarding the hydrogenation of C=C bonds. The influence of the support on the catalytic performance of the prepared Ni-based nanocomposites is particularly highlighted.

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.

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(L1 )2 (py)2 ][B(Ph)4 ]⋅py (1), [Dy(L1 )2 Cl(DME)] ⋅ 0.5DME (2) and [Dy(L2 )2 Cl] ⋅ 2.5(C7 H8 ) (3) (HL1 =Phenol, 2,4-bis(1,1-dimethylethyl)-6-[[(2-methoxy-5-methylphenyl)imino]methyl]; HL2 =Phenol, 2,4-bis(1,1-dimethylethyl)-6-[[(2-methoxyphenyl)imino]methyl]). The coordination environment of the Dy3+ ion and the direction of the anisotropic axis may be controlled by the combination of the substituent groups of the Schiff bases, the nature of the counter-ions (Cl- vs. BPh4 - ) and the coordinative solvent molecules. A zero-field slow relaxation of the magnetization is evidenced for all complexes but strong differences in the relaxation dynamics are observed depending on the Dy3+ site geometry. In this sense, complex 1 exhibits an anisotropy barrier of 472 cm-1 , which may be favourably compared to other related examples due to the shortening of the Dy-O bond in the axial direction. Besides, the three complexes exhibit a ligand-based luminescence making them as bifunctional magneto-luminescent systems.

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. The properties of this molecular material suggest that it may be competitive with inorganic magnetoelectrics.

Gold@Prussian blue analogue core-shell nanoheterostructures: their optical and magnetic properties.

Au@Prussian-Blue Analogue (PBA) shell nanoheterostructures are multifunctional nano-objects combining optical properties (surface plasmon resonance) of the Au core and magnetic properties of the PBA shell. We report in this article a series of new Au core@PBA shell nano-objects with different PBA shells: Au@K/Co/[FeII(CN)6] (2) and Au@K/Ni/[CrIII(CN)6]:[FeII(CN)6] (3) single PBA shell, as well as Au@K/Ni/[FeII(CN)6]@K/Ni/[FeIII(CN)6] (4) double PBA shell and Au@K/Ni/[FeII(CN)6]@K/Ni/[FeIII(CN)6]@K/Ni/[CrIII(CN)6] (5) triple PBA shell systems. The position and intensity of the Au SPR band, as well as the magnetic behaviour of the nanoheterostructures, are strongly affected by the shell composition and its thickness.

Making Prussian blue analogues nanoparticles luminescent: effect of the luminophore confinement over the properties.

In this communication, we report the post-synthetic functionalization of K+/Ni2+/[Cr(CN)6]3- Prussian blue analogue (PBA) nanoparticles by the 2-aminoanthracene luminophore to yield a bifunctional magneto-luminescent nanosystem. The photoluminescence properties of the fluorophore are found modified by the confinement effect upon adsorption, while the magnetic behavior of PBA is preserved.

Single-molecule magnet behaviour in a Dy(iii) pentagonal bipyramidal complex with a quasi-linear Cl-Dy-Cl sequence.

We report the synthesis and magnetic investigation of a dysprosium pentagonal bipyramidal complex [Dy(THF)5Cl2][BPh4] (1) exhibiting a linear Cl-Dy-Cl sequence suitable for providing a coordination environment allowing a zero-field slow relaxation of the magnetization. Besides, the complex also shows dual luminescence originating from [BPh4]- and Dy3+.