Compression of curium pyrrolidine-dithiocarbamate enhances covalency.

Curium is unique in the actinide series because its half-filled 5f 7 shell has lower energy than other 5f n configurations, rendering it both redox-inactive and resistant to forming chemical bonds that engage the 5f shell1-3. This is even more pronounced in gadolinium, curium's lanthanide analogue, owing to the contraction of the 4f orbitals with respect to the 5f orbitals4. However, at high pressures metallic curium undergoes a transition from localized to itinerant 5f electrons5. This transition is accompanied by a crystal structure dictated by the magnetic interactions between curium atoms5,6. Therefore, the question arises of whether the frontier metal orbitals in curium(III)-ligand interactions can also be modified by applying pressure, and thus be induced to form metal-ligand bonds with a degree of covalency. Here we report experimental and computational evidence for changes in the relative roles of the 5f/6d orbitals in curium-sulfur bonds in [Cm(pydtc)4]- (pydtc, pyrrolidinedithiocarbamate) at high pressures (up to 11 gigapascals). We compare these results to the spectra of [Nd(pydtc)4]- and of a Cm(III) mellitate that possesses only curium-oxygen bonds. Compared with the changes observed in the [Cm(pydtc)4]- spectra, we observe smaller changes in the f-f transitions in the [Nd(pydtc)4]- absorption spectrum and in the f-f emission spectrum of the Cm(III) mellitate upon pressurization, which are related to the smaller perturbation of the nature of their bonds. These results reveal that the metal orbital contributions to the curium-sulfur bonds are considerably enhanced at high pressures and that the 5f orbital involvement doubles between 0 and 11 gigapascal. Our work implies that covalency in actinides is complex even when dealing with the same ion, but it could guide the selection of ligands to study the effect of pressure on actinide compounds.

Infrared Resonance Raman of Bilayer Graphene: Signatures of Massive Fermions and Band Structure on the 2D Peak.

Few-layer graphene possesses low-energy carriers that behave as massive Fermions, exhibiting intriguing properties in both transport and light scattering experiments. Lowering the excitation energy of resonance Raman spectroscopy down to 1.17 eV, we target these massive quasiparticles in the split bands close to the K point. The low excitation energy weakens some of the Raman processes that are resonant in the visible, and induces a clearer frequency-separation of the substructures of the resonance 2D peak in bi- and trilayer samples. We follow the excitation-energy dependence of the intensity of each substructure, and comparing experimental measurements on bilayer graphene with ab initio theoretical calculations, we trace back such modifications on the joint effects of probing the electronic dispersion close to the band splitting and enhancement of electron-phonon matrix elements.

Organoarsonates Enable Single-Site Condensation of Hexalacunary {P2W12} Polyoxotungstates.

A systematic study of the condensation reactions of arylarsonic-functionalized [α-P2W12O48]14- units in acidic aqueous media identified that the specific presence of an amino group in the ortho position of the phenyl rings induces a dimerization process that allowed isolation of discrete dimeric polyanions [(o-H2N-C6H4-AsO3)4P4W24O85]14- (1) with an unprecedented polyoxometalate skeleton characterized by two seminal {P2W12} groups joined via a single W-O-W bridge. At the same time, addition of divalent transition metal ions (MnII, CoII, and NiII) in the reaction mixture directed a condensation process on a completely different pathway resulting in one-dimensional (1D) coordination polymers based on V-shaped [{M(H2O)4}P4W24O92(C6H6AsNO)2]14- polyanions (M = MnII (2), CoII (3), and NiII (4)). All polyanions were isolated as hydrated mixed potassium/dimethylammonium salts and thoroughly characterized in the solid state. 31P NMR studies showed that the discrete cluster 1 is comparatively stable in 1 M LiCl aqueous solution and thus represents a potential precursor for subsequent reactions.

Probing Enhanced Electron-Phonon Coupling in Graphene by Infrared Resonance Raman Spectroscopy.

We report on resonance Raman spectroscopy measurements with excitation photon energy down to 1.16 eV on graphene, to study how low-energy carriers interact with lattice vibrations. Thanks to the excitation energy close to the Dirac point at K, we unveil a giant increase of the intensity ratio between the double-resonant 2D and 2D^{'} peaks with respect to that measured in graphite. Comparing with fully ab initio theoretical calculations, we conclude that the observation is explained by an enhanced, momentum-dependent coupling between electrons and Brillouin zone-boundary optical phonons. This finding applies to two-dimensional Dirac systems and has important consequences for the modeling of transport in graphene devices operating at room temperature.

Controlled Hydrolysis of Phosphate Esters: A Route to Calixarene-Supported Rare-Earth Clusters.

Phosphate ester bonds are widely present in nature (e. g. DNA/RNA) and can be extremely stable against hydrolysis without the help of catalysts. Previously, we showed how the combination of phosphoryl and calix[4]arene moieties in the same organic framework (LPO ) allows isolation of single lanthanide (Ln) metal ions as [LnIII (LPO )2 ](O3 SCF3 )3 . Here we report how by controlling the reaction conditions a new hydrolyzed phosphoryl-calix[4]arene ligand (H3 LHPO ) is formed as a result of LnIII -mediated P-OEt bond cleavage in three out of the eight possible sites in LPO . The chelating nature of H3 LHPO traps the LnIII species in the form of [LnIII (LHPO )((EtO)2 P(O)OH)]2 dimers (Ln=La, Dy, Tb, Gd), where the Dy derivative shows slow magnetization relaxation. The strategy presented herein could be extended to access a broader library of hydrolyzed platforms (Hx LHPO ; x=1-8) that may represent mimics of nuclease enzymes.

Chemically detaching hBN crystals grown at atmospheric pressure and high temperature for high-performance graphene devices.

In this work, we report on the growth of hexagonal boron nitride (hBN) crystals from an iron flux at atmospheric pressure and high temperature and demonstrate that (i) the entire sheet of hBN crystals can be detached from the metal in a single step using hydrochloric acid and that (ii) these hBN crystals allow to fabricate high carrier mobility graphene-hBN devices. By combining spatially-resolved confocal Raman spectroscopy and electrical transport measurements, we confirm the excellent quality of these crystals for high-performance hBN-graphene-based van der Waals heterostructures. The full width at half maximum of the graphene Raman 2D peak is as low as 16 cm-1, and the room temperature charge carrier mobilitiy is around 80 000 cm2/(Vs) at a carrier density 1 × 1012cm-12. This is fully comparable with devices of similar dimensions fabricated using crystalline hBN synthesized by the high pressure and high temperature method. Finally, we show that for exfoliated high-quality hBN flakes with a thickness between 20 and 40 nm the line width of the hBN Raman peak, in contrast to the graphene 2D line width, is not useful for benchmarking hBN in high mobility graphene devices.

Structural Phase Transitions and Magnetic Superexchange in MI AgII F3 Perovskites at High Pressure.

Pressure-induced phase transitions of MI AgII F3 perovskites (M=K, Rb, Cs) have been predicted theoretically for the first time for pressures up to 100 GPa. The sequence of phase transitions for M=K and Rb consists of a transition from orthorhombic to monoclinic and back to orthorhombic, associated with progressive bending of infinite chains of corner-sharing [AgF6 ]4- octahedra and their mutual approach through secondary Ag⋅⋅⋅F contacts. In stark contrast, only a single phase transition (tetragonal→triclinic) is predicted for CsAgF3 ; this is associated with substantial deformation of the Jahn-Teller-distorted first coordination sphere of AgII and association of the infinite [AgF6 ]4- chains into a polymeric sublattice. The phase transitions markedly decrease the coupling strength of intra-chain antiferromagnetic superexchange in MAgF3 hosts lattices.

Cyclodextrin-Templated Co(II) Grids: Symmetry Control over Supramolecular Topology and Magnetic Properties.

While inherent complexation properties and propensity for self-organization of cyclodextrins (CDs) render them potentially promising scaffolds of magnetic materials, this research area is still at an embryonic stage. We report on the synthesis and structure characterization of a new sandwich-type complex, [(α-CD)2Co3Li6(H2O)9] (α-1), which represents a smaller analogue of the previously characterized [(γ-CD)2Co4Li8(H2O)12] (γ-1) cluster. A comprehensive structural analysis of α-1 and a careful reinvestigation of γ-1 reveal how the symmetry of CD ligands determines the molecular composition and supramolecular arrangements of Co/Li sandwich-type complexes. Furthermore, the first comparative studies of the magnetic properties in this type of system point to subtle differences in the magnetic behavior of both compounds. The sandwich-type complexes α-1 and γ-1 exhibit field-induced slow magnetic relaxation, defining a new family of magnetic materials with a pillared grid-like supramolecular structure composed of weakly interacting CoII centers forming an SMM.

Tetrahedral M4(µ4-O) Motifs Beyond Zn: Efficient One-Pot Synthesis of Oxido-Amidate Clusters via a Transmetalation/Hydrolysis Approach.

While zinc µ4-oxido-centered complexes are widely used as versatile precursors and building units of functional materials, the synthesis of their analogues based on other transition metals is highly underdeveloped. Herein, we present the first efficient systematic approach for the synthesis of homometallic [M4(µ4-O)L6]-type clusters incorporating divalent transition-metal centers, coated by bridging monoanionic organic ligands. As a proof of concept, we prepared a series of charge-neutral metal-oxido benzamidates, [M4(µ4-O) (NHCOPh)6] (M = Fe, Co, Zn), including iron(II) and cobalt(II) clusters not accessible before. The resulting complexes were characterized using elemental analysis, FTIR spectroscopy, magnetic measurements, and single-crystal X-ray diffraction. Detailed structural analysis showed interesting self-assembly of the tetrahedral clusters into 2D honeycomb-like supramolecular layers driven by hydrogen bonds in the proximal secondary coordination sphere. Moreover, we modeled the magnetic properties of new iron (II) and cobalt (II) clusters, which display a general tendency for antiferromagnetic coupling of the µ4-O/µ-benzamidate-bridged metal centers. The developed synthetic procedure is potentially easily extensible to other M(II)-oxido systems, which will likely pave the way to new oxido clusters with interesting optoelectronic and self-assembly properties and, as a result, will allow for the development of new functional materials not achievable before.

Ag(II) as Spin Super-Polarizer in Molecular Spin Clusters.

Using quantum mechanical calculations, we examine magnetic (super)exchange interactions in hypothetical, chemically reasonable molecular coordination clusters containing fluoride-bridged late transition metals or selected lanthanides, as well as Ag(II). By referencing to analogous species comprising closed-shell Cd(II), we provide theoretical evidence that the presence of Ag(II) may modify the magnetic properties of such systems (including metal-metal superexchange) to a surprising degree, specifically both coupling sign and strength may markedly change. Remarkably, this happens in spite of the fact that the fluoride ligand is the least susceptible to spin polarization among all monoatomic ligands known in chemistry. In an extreme case of an oxo-bridged Ni(II)2 complex, the presence of Ag(II) leads to a nearly 17-fold increase of magnetic superexchange and switching from antiferro (AFM)- to ferromagnetic (FM) coupling. Ag(II)─with one hole in its d shell that may be shared with or transferred to ligands─effectively acts as spin super-polarizer, and this feature could be exploited in spintronics and diverse molecular devices.

Polyoxotungstate Archetype {P4 W27 } and its 3d Derivatives.

The propensity of the new, phenylphosphonate-stabilized polyoxotungstate [(C6 H5 PV O)2 P4 W24 O92 ]16- to act as a precursor for new 3d metal-functionalized polyanions has been investigated. Reactions with MnII and CuII induce the formation of the previously unknown polyoxotungstate archetype {P4 W27 }, isolated as salts of the polyanions [Na⊂{MnII (H2 O)}{WO(H2 O)}P4 W26 O98 ]13- (1) and [K⊂{CuII (H2 O)}{W(OH)(H2 O)}P4 W27 O99 ]14- (2), which were characterized in the solid state (single-crystal X-ray diffraction, elemental and TG analyses, IR spectroscopy, SQUID magnetometry) and in aqueous solution (UV/Vis spectroscopy, cyclic voltammetry).

Trigonal Prismatic Coordination of Discrete Rare Earth Ions, Enforced by the Polyoxotungstate [P4 W27 O99 (H2 O)]16.

A family of solution-stable polyanions [Na⊂{LnIII (H2 O)}{WVI O(H2 O)}PV 4 WVI 26 O98 ]12- (Ln=Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and Y) represent the first examples of polyoxometalates comprising a single lanthanide(III) or yttrium(III) ion in a rare trigonal prismatic O6 environment. Their synthesis exploits the reactivity of the organophosphonate-functionalized precursor [P4 W24 O92 (C6 H5 PV O)2 ]16- with heterometal ions and yields hydrated potassium or mixed lithium/potassium salts of composition Kx Lny H12-x-y [Na⊂{Ln(H2 O)}{WO(H2 O)}P4 W26 O98 ]⋅nH2 O⋅mLiCl (x=8.5-11; y=0-2; n=24-34; m=0-1.5). The Dy, Ho, Er and Yb derivatives are characterized by slow magnetization relaxation.

Expansion of Zirconium Oxide Clusters by 3d/4f Ions.

Two series of charge-neutral coordination clusters featuring quasi-isostructural metal oxide cores, isolated as [Zr6Fe2Ln2O8(ib)14(bda)2(NO3)2]·xMeCN (Ln = La (1), Ce (2), Pr (3), and Nd (4); ib- = isobutyrate; H2bda = N-butyldiethanolamine) and [Zr6Fe2Ln2O8(ib)14(mda)2(NO3)2]·xMeCN (Ln = La (5), Ce (6), Pr (7), and Nd (8); H2mda = N-methyldiethanolamine), were obtained via one-pot reactions of [Fe3O(ib)6(H2O)3]NO3 as a critical precursor, Ln(NO3)3·6H2O (Ln = La, Ce, Pr, and Nd), the respective aminoalcohol, and [Zr6O4(OH)4(ib)12(H2O)]·3Hib in an acetonitrile solution. The coordination clusters in 1-8 feature {Zr6O8} cores that are structurally expanded by two 4f (Ln3+) and two 3d (Fe3+) metal ions, each individually coordinated to one of the eight oxide centers of {Zr6O8}, producing a metal skeleton where the 3d/4f positions cap four of the triangular faces of the central Zr6 octahedron. The coordination clusters differ in the chosen aminoalcohol coligands, N-butyldiethanolamine or N-methyldiethanolamine, which lead to a different isobutyrate coordination pattern in the two series, while the {Fe2Ln2Zr6O8} core structure remains virtually unaffected. All eight coordination clusters are obtained in moderate to good yields of 29-66% after only several days. Complexes 1-8 are stable against air and moisture; they are also surprisingly thermally stable up to 280 °C in air and in nitrogen atmosphere, and they represent the first reported examples of 3d/4f-functionalized zirconium oxide clusters.

Insertion of VIV Ions into the Polyoxotungstate Archetype {As4W40}.

A new polyoxometalate compound consisting of the 39-tungsto-4-arsenate(III) unit with four incorporated VIV ions, isolated as (NH4)22[(VIVO)2(VIVO(H2O))(AsIIIWVI9O33)2(AsIIIWVI8.5VIV0.5(OH)O32)2(WVIO2)4]·48H2O (NH4-As4W39(V4)), was synthesized and fully characterized. SQUID magnetometry shows three weakly coupled VIV centers with an antiferromagnetic exchange interaction and one isolated VIV ion as a spin-1/2 Curie paramagnet. UV-vis spectroscopy indicates that the As4W39(V4) structure remains intact in aqueous solution for at least 24 h. To enable the deposition of As4W39(V4) from solution on gold surfaces, its trihexyltetradecylphosphonium salt, THTDP-As4W39(V4), was prepared. The IR spectra of both congeners reveal the structural identity of As4W39(V4) independent of the countercations. The X-ray absorption near-edge structure data confirm the presence of VIV centers in a distorted square-pyramidal coordination geometry in NH4-As4W39(V4) and THTDP-As4W39(V4). X-ray photoelectron spectroscopy of the latter, deposited on Au(111), shows that the 4 V and 35 W centers preserve their IV+ and VI+ oxidation states, while the remaining 4 W ions are reduced to IV+.

Magnetic Phase Transitions in a Ni4 O4 -Cubane-Based Metal-Organic Framework.

An unprecedented spin cluster-based network architecture {[NiII 2 (pdaa)(OH)2 (H2 O)]n (H2 pdaa=1,4-phenylene diacetic acid)}, comprising 1D linear chains of NiII ions crosslinked via Ni4 O4 cubanes, forms under hydrothermal conditions; this 3D coordination network exhibits magnetic ordering at 23.9 K as well as a second magnetic ordering process at 2.8 K likely associated with a structural phase transition.

Unusually Distorted Pseudo-Octahedral Coordination Environment Around CoII from Thioether Schiff Base Ligands in Dinuclear [CoLn] (Ln = La, Gd, Tb, Dy, Ho) Complexes: Synthesis, Structure, and Understanding of Magnetic Behavior.

The synthesis, structural characterization, and magnetic behavior of a new family of binuclear CoII-LnIII complexes of formula [LnIIICoIIL2(NO3)3]·H2O (Ln = La, 1; Gd, 2; Tb, 3; Dy, 4; Ho, 5; HL = 3-methoxy-N-(2-(methylsulfanyl)phenyl)salicylaldimine) have been reported. The chosen ligand system HL has adjacent soft ONS and hard OO binding pockets ideal for selective coordination of CoII and 4f metal ions. All the complexes 1-5 exhibit a CoII center in a highly distorted octahedral geometry with the LnIII centers in bicapped square-antiprism geometry. The unique distortion about the CoII center is introduced by the coordination of 4f metal ions in the hard OO coordination site. The distortion is further supported by the presence of -SMe groups giving an S donor atom which owing to its larger size can support large bond distances and angles. The geometry around the CoII centers is intermediate between meridional and facial geometric isomers. The magnetic properties of these complexes have been investigated by a "full model" approach using CONDON with the experimental magnetochemical analysis revealing ferromagnetic Co-Ln coupling in compounds 2-5. Ab initio calculations on the X-ray crystal structures of 1-5 paint a semiquatitative picture about the contribution of the individual anisotropic centers toward the overall magnetic properties of the compounds. Theoretical analysis predicts 1 and 2 as weak single-ion magnet (SIM) and single-molecule magnet (SMM) respectively with CoII being solely responsible for the complex anisotropy. In 2, JCoGd plays a crucial role in preserving the anisotropy contribution of Co by channelizing relaxation via a higher excited exchange doublet. Because of the inefficiency of JCoTb, JCoDy, and JCoHo in quenching single-ion Ln fragment transverse anisotropy and preserving CoII high axial anisotropy (favoring rhombicity), 3-5 lack SMM behavior.

Lanthanide-Containing 22-Tungsto-2-germanates [Ln(GeW11O39)2]13-: Synthesis, Structure, and Magnetic Properties.

We report on the synthesis and structural characterization of two series of lanthanide-containing 22-tungsto-2-germanates. The first series corresponds to a family of polyanions with the formula [Ln(ß2-GeW11O39)2]13- (LnIII = La (1), Ce (2), Pr (3), Nd (4), Sm (5), Gd (6), Dy (7)), and the second series corresponds to a family with the formula [Ln(ß2-GeW11O39)(α-GeW11O39)]13- (LnIII = Ho (8), Er (9), Tm (10)). All compounds were characterized in the solid state by single-crystal and powder XRD, IR, TGA, and SQUID magnetometry. The polyanions were synthesized in aqueous medium by direct reaction of the monolacunary [ß2-GeW11O39]8- POM precursor with the corresponding lanthanide salts. The structure of the polyanions consists of an 8-coordinated lanthanide ion in a square-antiprismatic geometry, which is sandwiched either between two [ß2-GeW11O39]8- units for 1-7 or between a [ß2-GeW11O39]8- and a [α-GeW11O39]8- unit for 8-10. Furthermore, the effect of the central paramagnetic lanthanide ion on the magnetic behavior of the polyanions was investigated, with the erbium-derivative [Er(ß2-GeW11O39)(α-GeW11O39)]13- (9) showing single-molecule magnet (SMM) behavior.

Size-isolation of superparamagnetic iron oxide nanoparticles improves MRI, MPI and hyperthermia performance.

Superparamagnetic iron oxide nanoparticles (SPION) are extensively used for magnetic resonance imaging (MRI) and magnetic particle imaging (MPI), as well as for magnetic fluid hyperthermia (MFH). We here describe a sequential centrifugation protocol to obtain SPION with well-defined sizes from a polydisperse SPION starting formulation, synthesized using the routinely employed co-precipitation technique. Transmission electron microscopy, dynamic light scattering and nanoparticle tracking analyses show that the SPION fractions obtained upon size-isolation are well-defined and almost monodisperse. MRI, MPI and MFH analyses demonstrate improved imaging and hyperthermia performance for size-isolated SPION as compared to the polydisperse starting mixture, as well as to commercial and clinically used iron oxide nanoparticle formulations, such as Resovist® and Sinerem®. The size-isolation protocol presented here may help to identify SPION with optimal properties for diagnostic, therapeutic and theranostic applications.

Kinetics and Mechanism of Pyrrolidine Buffer-Catalyzed Fulvene Formation.

Rapid synthesis of fulvenes is achieved using pyrrolidinium/pyrrolidine buffers in anhydrous acetonitrile. Time-dependent UV-vis absorption and NMR spectroscopy reveal that the rate and yield of fulvene formation depend strongly on both the presence of acid in the medium and the choice of solvent, and they are negatively affected by water. Kinetic data have been collected for various substrates, and the synthetic benefits of the adjusted reaction conditions are showcased. Enhancements of reaction rates are found in comparison to literature procedures. α-Unsaturated fulvenes that were previously difficult to access can now be obtained in good yields.

Sequential Isomerization of a Macrocyclic Polyoxometalate Archetype.

Controlled isomerization of individual {α-P2W12O48} polyoxotungstate building blocks under the constricted conditions of the macrocyclic [P8W48O184]40- archetype ({P8W48}) is linked to site-specific CuII coordination. The derivatives [αγαγ-P8W48O184{Cu(H2O)}2]36- (1), [γγγγ-P8W48O184{Cu(H2O)0.5}4]32- (2), and [αγγγ-P8W48O184{Cu(H2O)}3]34- (3) feature the {αγαγ-P8W48} and the hitherto unknown {γγγγ-P8W48} and {αγγγ-P8W48} isomers based on {α-P2W12} and/or CuII-stabilized {γ-P2W12} units and form from the reactions of the classical {P8W48} (={αααα-P8W48}) and CuCl2 in sodium acetate medium (pH 5.2). All products were thoroughly characterized in both the solid state and aqueous solutions, including electrocatalysis assessments.