4f Metals Research Articles

A hard molecular nanomagnet from confined paramagnetic 3d-4f spins inside a fullerene cage

Reducing inter-spin distance can enhance magnetic interactions and allow for the realization of outstanding magnetic properties. However, achieving reduced distances is technically challenging. Here, we construct a 3d-4f metal cluster (Dy2VN) inside a C80 cage, affording a heretofore unseen metallofullerene containing both paramagnetic 3d and 4f metal ions. The significantly suppressed 3d-4f (Dy-V) distances, due to the unique cage confinement effect, were observed by crystallographic and theoretical analysis of Dy2VN@Ih(7)-C80. These reduced distances result in an enhanced magnetic coupling (Jtotal, Dy-V = 53.30 cm−1; Jtotal, Dy-Dy = −6.25 cm−1), leading to a high magnetic blocking temperature compared to reported 3d-4f single-molecule magnets and strong coercive field of 2.73 Tesla. Our work presents a new class of single-molecule magnets with both paramagnetic 3d and 4f metals confined in a fullerene cage, offering superior and tunable magnetic properties due to the unique cage confinement effect and the diverse composition of the entrapped magnetic core.

Highlighting Recent Crystalline Engineering Aspects of Luminescent Coordination Polymers Based on F-Elements and Ditopic Aliphatic Ligands.

Three principal factors may influence the final structure of coordination polymers (CPs): (i) the nature of the ligand, (ii) the type and coordination number of the metal center, and (iii) the reaction conditions. Further, flexible carboxylate aliphatic ligands have been widely employed as building blocks for designing and synthesizing CPs, resulting in a diverse array of materials with exciting architectures, porosities, dimensionalities, and topologies as well as an increasing number of properties and applications. These ligands show different structural features, such as torsion angles, carbon backbone number, and coordination modes, which affect the desired products and so enable the generation of polymorphs or crystalline phases. Additionally, due to their large coordination numbers, using 4f and 5f metals as coordination centers combined with aliphatic ligands increases the possibility of obtaining different crystal phases. Additionally, by varying the synthetic conditions, we may control the production of a specific solid phase by understanding the thermodynamic and kinetic factors that influence the self-assembly process. This revision highlights the relationship between the structural variety of CPs based on flexible carboxylate aliphatic ligands and f-elements (lanthanide and actinides) and their outstanding luminescent properties such as solid-state emissions, sensing, and photocatalysis. In this sense, we present a structural analysis of the CPs reported with the oxalate ligand, as the one rigid ligand of the family, and other flexible dicarboxylate linkers with –CH2– spacers. Additionally, the nature of the luminescence properties of the 4f or 5f-CPs is analyzed, and finally, we present a novel set of CPs using a glutarate-derived ligand and samarium, with the formula [2,2′-bipyH][Sm(HFG)2 (2,2′-bipy) (H2O)2]•(2,2′-bipy) (α-Sm) and [2,2′-bipyH][Sm(HFG)2 (2,2′-bipy) (H2O)2] (β-Sm).

Synergistic Experimental and Theoretical Studies of Luminescent-Magnetic Ln2Zn6 Clusters.

The present work is part of our ongoing quest for developing functional inorganic complexes using unorthodox pyridyl-pyrazolyl-based ligands. Accordingly, we report herein the synthesis, characterization, and luminescence and magnetic properties of four 3d-4f mixed-metal complexes with a general core of Ln2Zn6 (Ln = Dy, Gd, Tb, and Eu). In stark contrast to the popular wisdom of using a compartmental ligand with separate islands of hard and soft coordinating sites for selective coordination, we have vindicated our approach of using a ligand with overcrowded N-coordinating sites that show equal efficiency with both 4f and 3d metals toward multinuclear cage-cluster formation. The encouraging red and green photolumiscent features of noncytotoxic Eu2Zn6 and Tb2Zn6 complexes along with their existence in nanoscale dimension have been exploited with live-cell confocal microscopy imaging of human breast adenocarcinoma (MCF7) cells. The magnetic features of the Dy2Zn6 complex confirm the single-molecule-magnet behavior with befitting frequency- and temperature-dependent out-of-phase signals along with an Ueff value of ∼5 K and a relaxation time of 8.52 × 10-6 s. The Gd2Zn6 complex, on the other hand, shows cryogenic magnetic refrigeration with an entropy change of 11.25 J kg-1 K-1 at a magnetic field of 7 T and at 2 K. Another important aspect of this work reflects the excellent agreement between the experimental results and theoretical calculations. The theoretical studies carried out using the broken-symmetry density functional theory, ORCA suite of programs, and MOLCAS calculations using the complete-active-space self-consistent-field method show an excellent synergism with the experimentally measured magnetic and spectroscopic data.

Precision Engineering of 2D Protein Layers as Chelating Biogenic Scaffolds for Selective Recovery of Rare-Earth Elements.

Rare-earth elements, which include the lanthanide series, are key components of many clean energy technologies, including wind turbines and photovoltaics. Because most of these 4f metals are at high risk of supply chain disruption, the development of new recovery technologies is necessary to avoid future shortages, which may impact renewable energy production. This paper reports the synthesis of a non-natural biogenic material as a potential platform for bioinspired lanthanide extraction. The biogenic material takes advantage of the atomically precise structure of a 2D crystalline protein lattice with the high lanthanide binding affinity of hydroxypyridinonate chelators. Luminescence titration data demonstrated that the engineered protein layers have affinities for all tested lanthanides in the micromolar-range (dissociation constants) and a higher binding affinity for the lanthanide ions with a smaller ionic radius. Furthermore, competitive titrations confirmed the higher selectivity (up to several orders of magnitude) of the biogenic material for lanthanides compared to other cations commonly found in f-element sources. Lastly, the functionalized protein layers could be reused in several cycles by desorbing the bound metal with citrate solutions. Taken together, these results highlight biogenic materials as promising bioadsorption platforms for the selective binding of lanthanides, with potential applications in the recovery of these critical elements from waste.

Bond dissociation energies of lanthanide sulfides and selenides.

Resonant two-photon ionization spectroscopy has been employed to observe sharp predissociation thresholds in the spectra of the lanthanide sulfides and selenides for the 4f metals Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, and Lu. As these molecules possess a large density of electronic states near the ground separated atom limit, these predissociation thresholds are argued to coincide with the true 0 K bond dissociation energies (BDEs). This is because spin-orbit and nonadiabatic couplings among these states allow the molecules to predissociate rapidly when the BDE is reached or exceeded. The measured BDEs, in eV, are as follows: 5.230(3) (PrS), 4.820(3) (NdS), 4.011(17) (SmS), 3.811(8) (EuS), 5.282(5) (GdS), 5.292(3) (TbS), 4.298(3) (DyS), 4.251(3) (HoS), 4.262(3) (ErS), 5.189(3) (LuS), 4.496(3) (PrSe), 4.099(3) (NdSe), 3.495(17) (SmSe), 3.319(3) (EuSe), 4.606(3) (GdSe), 4.600(6) (TbSe), 3.602(3) (DySe), 3.562(3) (HoSe), 3.587(3) (ErSe), and 4.599(6) (LuSe). Through the use of thermochemical cycles, the 0 K gaseous heat of formation, ΔfH0K ○, is reported for each molecule. A threshold corresponding to the onset of two-photon ionization in EuSe was also observed, providing the ionization energy of EuSe as 6.483(10) eV. Through a thermochemical cycle and the above reported BDE of the neutral EuSe molecule, the BDE for the Eu+-Se cation was also determined as D0(Eu+-Se) = 2.506(10) eV. Bonding trends of the lanthanide sulfides and selenides are discussed. Our previous observation that the transition metal sulfides are 15.6% more strongly bound than the corresponding selenides continues to hold true for the lanthanides as well.

Molecular Oxygen-Induced Ferromagnetism and Half-Metallicity in α-BaNaO4: A First-Principles Study.

Molecular oxygen resembles 3d and 4f metals in exhibiting long-range spin ordering and strong electron correlation behaviors in compounds. Ferromagnetic spin ordering and half-metallicity, however, are quite elusive and have not been well acknowledged. In this Article, we address this issue by studying how spins will interact with each other if the oxygen dimers are arranged in a different way from that in the known superoxides and peroxides by first-principles calculations. Based on the results of a structure search, thermodynamic studies, and lattice dynamics, we show that tetragonal α-BaNaO4 is a stable half-metal with a Curie temperature at 120 K, the first example in this class of compounds. Like 3d and 4f metals, the O2 dimer carries a local magnetic moment of 0.5 μB due to the unpaired electrons in its π* orbitals. This compound can be regarded as forming from the O2 dimer layers stacking in a head-to-head way. In contrast to the arrangement in AO2 (A = K, Rb, Cs), the spins are ferromagnetically coupled both within and between the layers. Spin polarization occurs in π* orbitals, with spin-up electrons fully occupying the valence band and spin-down electrons partially occupying the conduction band, forming semiconducting and metallic channels, respectively. Our results highlight the importance of geometric arrangement of O2 dimers in inducing ferromagnetism and other novel properties in O2-dimer-containing compounds.

Two heads are better than one: improving magnetic relaxation in the dysprosium metallocene upon dimerization by use of an exceptionally weakly-coordinating anion.

Partial metathesis between two weakly-coordinating anions in the archetypical dysprosium metallocene results in the first example of [BPh4]- as a bridging ligand in 4f metals, with a unique η2,η2:η2,η2-bridge. Magnetic susceptibility and relaxation dynamics studies along with ab initio calculations reveal improved slow relaxation of the magnetization in over its mononuclear congener, resulting in an energy barrier of 490 K/340 cm-1 and waist-restricted hysteresis up to 6.5 K.

Engineering electronic structure to prolong relaxation times in molecular qubits by minimising orbital angular momentum

The proposal that paramagnetic transition metal complexes could be used as qubits for quantum information processing (QIP) requires that the molecules retain the spin information for a sufficient length of time to allow computation and error correction. Therefore, understanding how the electron spin-lattice relaxation time (T1) and phase memory time (Tm) relate to structure is important. Previous studies have focused on the ligand shell surrounding the paramagnetic centre, seeking to increase rigidity or remove elements with nuclear spins or both. Here we have studied a family of early 3d or 4f metals in the +2 oxidation states where the ground state is effectively a 2S state. This leads to a highly isotropic spin and hence makes the putative qubit insensitive to its environment. We have studied how this influences T1 and Tm and show unusually long relaxation times given that the ligand shell is rich in nuclear spins and non-rigid.

Influence of the Size and Structural Factors on the Magnetism of Multilayer Films Based on 3d and 4f Metals

This work has presented some data on the layer structuring of films of 3d and 4f metals and their alloys, which have potential for practical use in magnetic sensors. The decrease in the thickness of magnetic layers with this structuring entails natural worsening of the crystallinity and leads to a degradation of magnetic ordering. However, the manifestation of these tendencies depends to a great extent on the conditions of preparation, the composition, and the sequence of the deposition of the contacting layers in the multilayer structures. The combination of these factors makes it possible to realize an optimum composition and optimum structural states of the films, which in a number of cases lead to the appearance of new combinations of functional properties.

Influence of Structure on Magnetic and Photoluminescent Properties of Coordination Compounds of 3d and 4f Metals and Nanocomposites Based on Them

Recent results in the field of molecular magnets and luminescent materials design are summarized. The principles for increasing the ground state multiplicity of polynuclear complexes and methods of conferring magnetic anisotropy onto molecular objects and nanoparticles are considered. The main attention is paid to the influence of the structure of coordination compounds and, in particular, the chemical structure of ligands on the photoluminescence characteristics of complexes. Aspects of the possible use of magneto-luminescent composites in biomedical studies are discussed. Further prospects of development in this field are considered.

Diagnostics of the plasma parameters based on the K X-ray line positions for various 4d and 4f metals

Abstract This paper shows the theoretical predictions of the outer-shell ionization effect on the positions of Kα1,2, Kβ1,3, and K β2 X-ray lines for some 4d-transition metals (molybdenum and palladium) and 4f rare-earth elements (dysprosium and ytterbium). The ionization energy shifts have been evaluated using the multiconfiguration Dirac-Fock method, containing Breit interaction and quantum electrodynamic (QED) corrections. The presented results are important for obtaining the information about some parameters of plasma generated by different sources, especially by pulsed power machine and short-pulse lasers.

Microstructural and magnetic properties of Ax:Zn1-xO (A=Mn, Gd and Mn/Gd) nanocrystals

We report the microstructural and magnetic properties of transition (3d) and rare earth (4f) metal substituted into the Ax:Zn1−xO (A=Mn, Gd and Mn/Gd) nanocrystal samples synthesized by solgel method. The structural properties and morphology of all samples have been analysed using X-ray diffraction (XRD) method and scanning electron microscopy. The impurity phase in the XRD patterns for all samples is not seen, except (Mn/Gd):ZnO sample where a very weak secondary phase of Gd2O3 is observed. Due to the large mismatch of the ionic radii between Mn2+ and Gd3+ ions, the strain inside the matrix increases, unlike the crystallite size decreases with the substitution of Mn and Gd into ZnO system. A couple of additional vibration modes due to the dopant have been observed in Raman spectrum. The magnetic properties have been studied by vibrating sample magnetometer. The magnetic hysteresis shows that Mn:ZnO and Gd:ZnO have soft ferromagnetic (FM) behaviour, whereas (Mn/Gd):ZnO has strong FM behaviour at room temperature (RT). The enhancement of ferromagnetism (FM) in (Mn/Gd):ZnO sample might be related to short-range FM coupling between Mn2+ and Gd3+ ions via defects potential and/or strain-induced FM coupling due to the expansion lattice by doping. The experimental results indicate that RTFM can be achieved by co-substitution of 3d and 4f metals in ZnO which can be used in spintronics applications.

Iridium- and Osmium-decorated Reduced Graphenes as Promising Catalysts for Hydrogen Evolution.

Renewable energy sources are highly sought after as a result of numerous worldwide problems concerning the environment and the shortage of energy. Currently, the focus in the field is on the development of catalysts that are able to provide water splitting catalysis and energy storage for the hydrogen evolution reaction (HER). While platinum is an excellent material for HER catalysis, it is costly and rare. In this work, we investigated the electrocatalytic abilities of various graphene-metal hybrids to replace platinum for the HER. The graphene materials were doped with 4f metals, namely, iridium, osmium, platinum and rhenium, as well as 3d metals, namely, cobalt, iron and manganese. We discovered that a few hybrids, in particular iridium- and osmium-doped graphenes, have the potential to become competent electrocatalysts owing to their low costs and-more importantly-to their promising electrochemical performances towards the HER. One of the more noteworthy observations of this work is the superiority of these two hybrids over MoS2 , a well-known electrocatalyst for the HER.

ChemInform Abstract: Spectroscopic and Magnetic Investigations of Actinide‐based Nanomagnets

AbstractReview: 31 refs.

Lanthanum complex of a multifunctional water-soluble siloxane compound—Synthesis, surface activity and applications for nanoparticles stabilization

A tris(hydroxymethyl)aminomethane-modified polysiloxane has previously been investigated for surface properties and valuable practical applications have been proposed, including nanoparticle stabilization, complexing of 3d metals, micellar solubilization of drugs and water dispersion of metal oxide nanoparticles. In this article we show the ability of this multifunctional polymer to bind 4f metals. A polymeric lanthanum complex was obtained and characterized. The most probable structure was assigned based on ESI-MS and FT-IR, using data obtained with a homologous disiloxane model compound. The polymeric lanthanum complex shows surface activity, with a CMC value of 150mg/L. Self-assembling in water was also studied by DLS and TEM, which revealed formation of vesicles. The La complex was tested with very good results for polymer nanoparticle stabilization. Polycarolactone nanoparticles of ca. 150nm with long-term stability (Zeta potential=55mV) were obtained. The aqueous dispersion of organic-coated metal oxide nanoparticles was also successful.

Spectroscopic and magnetic investigations of actinide‐based nanomagnets

Magnetic exchange is an essential feature of transition‐metal nanomagnets because it combines the relatively low spin‐only moments of several ions into a “giant spin” ground state, which can make slow magnetic relaxation very favorable in an axially anisotropic environment. In contrast, most of the early research on lanthanide‐based complexes focused on single‐ion magnets, where the required large moment is generated by the unquenched orbital contribution (which is parallel to the spin in heavy rare earths). With their unfilled 5f electronic shell being on the verge between localization and itinerancy, actinides are expected to combine the best of both 3d and 4f metals in terms of exchange and anisotropy, and are therefore under consideration as potential building blocks for the next generation of single‐molecule magnets. In this Perspective, a review of the recent development in this field is given, and some discrepancies between the spectroscopic and magnetic data are discussed. © 2014 European Commission. International Journal of Quantum Chemistry published by Wiley Periodicals, Inc.

A Stable Hybrid Bisphosphonate Polyoxometalate Single‐Molecule Magnet

A new functionalizable polyoxometalate platform: The heptanuclear CoII polyoxometalate complex [{(B-α- PW9O34)Co3(OH)(H2O)2(O3PC(O)- (C3H6NH3)PO3)}2Co]14− represents a unique example of a magnetic, stable, functionalizable polyoxotungstate platform, and behaves as a single-molecule magnet (see figure).

Room temperature ferromagnetism in Teflon due to carbon dangling bonds

The ferromagnetism in many carbon nanostructures is attributed to carbon dangling bonds or vacancies. This provides opportunities to develop new functional materials, such as molecular and polymeric ferromagnets and organic spintronic materials, without magnetic elements (for example, 3d and 4f metals). Here we report the observation of room temperature ferromagnetism in Teflon tape (polytetrafluoroethylene) subjected to simple mechanical stretching, cutting or heating. First-principles calculations indicate that the room temperature ferromagnetism originates from carbon dangling bonds and strong ferromagnetic coupling between them. Room temperature ferromagnetism has also been successfully realized in another polymer, polyethylene, through cutting and stretching. Our findings suggest that ferromagnetism due to networks of carbon dangling bonds can arise in polymers and carbon-based molecular materials.

Uranyl and/or Rare-Earth Mellitates in Extended Organic–Inorganic Networks: A Unique Case of Heterometallic Cation–Cation Interaction with UVI═O–LnIII Bonding (Ln = Ce, Nd)

A series of uranyl and lanthanide (trivalent Ce, Nd) mellitates (mel) has been hydrothermally synthesized in aqueous solvent. Mixtures of these 4f and 5f elements also revealed the formation of a rare case of lanthanide-uranyl coordination polymers. Their structures, determined by XRD single-crystal analysis, exhibit three distinct architectures. The pure lanthanide mellitate Ln(2)(H(2)O)(6)(mel) possesses a 3D framework built up from the connection of isolated LnO(6)(H(2)O)(3) polyhedra (tricapped trigonal prism) through the mellitate ligand. The structure of the uranyl mellitate (UO(2))(3)(H(2)O)(6)(mel)·11.5H(2)O is lamellar and consists of 8-fold coordinated uranium atoms linked to each other through the organic ligand giving rise to the formation of a 2D 3(6) net. The third structural type, (UO(2))(2)Ln(OH)(H(2)O)(3)(mel)·2.5H(2)O, involves direct oxygen bondings between the lanthanide and uranyl centers, with the isolation of a heterometallic dinuclear motif. The 9-fold coordinated Ln cation, LnO(5)(OH)(H(2)O)(3), is linked to the 7-fold coordinated uranyl (UO(2))O(4)(OH) (pentagonal bipyramid) via one μ(2)-hydroxo group and one μ(2)-oxo group. The latter is shared between the uranyl bonding (U═O = 1.777(4)/1.779(6) Å) and a long Ln-O bonding (Ce-O = 2.822(4) Å; Nd-O = 2.792(6) Å). This unusual linkage is a unique illustration of the so-called cation-cation interaction associating 4f and 5f metals. The dinuclear motif is then further connected through the mellitate ligand, and this generates organic-inorganic layers that are linked to each other via discrete uranyl (UO(2))O(4) units (square bipyramid), which ensure the three-dimensional cohesion of the structure. The mixed U-Ln carboxylate is thermally decomposed from 260 to 280 °C and then transformed into the basic uranium oxide (U(3)O(8)) together with U-Ln oxide with the fluorite structural type ("(Ln,U)O(2)"). At 1400 °C, only fluorite type "(Ln,U)O(2)" is formed with the measured stoichiometry of U(0.63)Ce(0.37)O(2) and U(0.60)Nd(0.40)O(2-δ).

3‐Hydroxypyridin‐2‐one Complexes of Near‐Infrared (NIR) Emitting Lanthanides: Sensitization of Holmium(III) and Praseodymium(III) in Aqueous Solution

PrIII- und HoIII-Komplexe des vierzähnigen Chromophors 1-Methyl-3-hydroxypyridin-2-on zeigen in wässriger Lösung charakteristische Emissionsbanden im sichtbaren Bereich und im nahen Infrarot. Der HoIII-Komplex wurde strukturell charakterisiert, und es wurde – erstmalig für einen HoIII-Komplex – auch die Abklingkinetik der NIR-Lumineszenz gemessen.