15 research outputs found
Organometallic neptunium(III) complexes
Studies of transuranic organometallic complexes provide a particularly valuable insight into covalent contributions to the metalâligand bonding, in which the subtle differences between the transuranium actinide ions and their lighter lanthanide counterparts are of fundamental importance for the effective remediation of nuclear waste. Unlike the organometallic chemistry of uranium, which has focused strongly on UIII and has seen some spectacular advances, that of the transuranics is significantly technically more challenging and has remained dormant. In the case of neptunium, it is limited mainly to NpIV. Here we report the synthesis of three new NpIII organometallic compounds and the characterization of their molecular and electronic structures. These studies suggest that NpIII complexes could act as single-molecule magnets, and that the lower oxidation state of NpII is chemically accessible. In comparison with lanthanide analogues, significant d- and f-electron contributions to key NpIII orbitals are observed, which shows that fundamental neptunium organometallic chemistry can provide new insights into the behaviour of f-elements
Molecular and electronic structure of terminal and alkali metal-capped uranium(V) nitride complexes
Determining the electronic structure of actinide complexes is intrinsically challenging because inter-electronic repulsion, crystal field, and spinâorbit coupling effects can be of similar magnitude. Moreover, such efforts have been hampered by the lack of structurally analogous families of complexes to study. Here we report an improved method to UâĄN triple bonds, and assemble a family of uranium(V) nitrides. Along with an isoelectronic oxo, we quantify the electronic structure of this 5f1 family by magnetometry, optical and electron paramagnetic resonance (EPR) spectroscopies and modelling. Thus, we define the relative importance of the spinâorbit and crystal field interactions, and explain the experimentally observed different ground states. We find optical absorption linewidths give a potential tool to identify spinâorbit coupled states, and show measurement of UV···UV super-exchange coupling in dimers by EPR. We show that observed slow magnetic relaxation occurs via two-phonon processes, with no obvious correlation to the crystal field
Giant coercivity and high magnetic blocking temperatures for N2 3â radical-bridged dilanthanide complexes upon ligand dissociation
Single-molecule magnets typically only retain information in the presence of an applied magnetic field and at very low temperatures. Here, Demir, Long and co-workers design N2 3â radical-bridged dilanthanide complexes that exhibit giant coercivities and 100-s magnetic blocking temperatures of up to 20âK
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An assessment of strategies for the development of solid-state adsorbents for vehicular hydrogen storage
Nanoporous adsorbents are a diverse category of solid-state materials that hold considerable promise for vehicular hydrogen storage. Although impressive storage capacities have been demonstrated for several materials, particularly at cryogenic temperatures, materials meeting all of the targets established by the U.S. Department of Energy have yet to be identified. In this Perspective, we provide an overview of the major known and proposed strategies for hydrogen adsorbents, with the aim of guiding ongoing research as well as future new storage concepts. The discussion of each strategy includes current relevant literature, strengths and weaknesses, and outstanding challenges that preclude implementation. We consider in particular metal-organic frameworks (MOFs), including surface area/volume tailoring, open metal sites, and the binding of multiple H2 molecules to a single metal site. Two related classes of porous framework materials, covalent organic frameworks (COFs) and porous aromatic frameworks (PAFs), are also discussed, as are graphene and graphene oxide and doped porous carbons. We additionally introduce criteria for evaluating the merits of a particular materials design strategy. Computation has become an important tool in the discovery of new storage materials, and a brief introduction to the benefits and limitations of computational predictions of H2 physisorption is therefore presented. Finally, considerations for the synthesis and characterization of hydrogen storage adsorbents are discussed
Complete Active Space Wavefunction-Based Analysis of Magnetization and Electronic Structure
International audienceA theoretical framework for the generation of natural orbitals, naturalspin orbitals, as well as orbital- and spin-magnetizations from multi-configurationalab-initio wavefunction calculations including spin-orbit coupling is presented. It isshown how these computational orbital and magnetization tools can be used to inter-pret and rationalize the magnetic properties of selected complexes containing tran-sition metals, lanthanides, and actinides
Magnetic Blocking in a Linear Iron(I) Complex
Single-molecule magnets that contain one spin centre may represent the smallest possible unit for spin-based computational devices. Such applications, however, require the realization of molecules with a substantial energy barrier for spin inversion, achieved through a large axial magnetic anisotropy. Recently, significant progress has been made in this regard by using lanthanide centres such as terbium(III) and dysprosium(III), whose anisotropy can lead to extremely high relaxation barriers. We contend that similar effects should be achievable with transition metals by maintaining a low coordination number to restrict the magnitude of the d-orbital ligand-field splitting energy (which tends to hinder the development of large anisotropies). Herein we report the first two-coordinate complex of iron(I), [Fe(C(SiMe3) 3)2]-, for which alternating current magnetic susceptibility measurements reveal slow magnetic relaxation below 29 K in a zero applied direct-current field. This S =complex exhibits an effective spin-reversal barrier of U eff = 226(4) cm-1, the largest yet observed for a single-molecule magnet based on a transition metal, and displays magnetic blocking below 4.5 K