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Themed collection New molecules and materials from the f-block

48 items
Open Access Feature Article

Lanthanide-based tools for the investigation of cellular environments

Coordination complexes and supramolecules based on trivalent lanthanides for probing biological systems, in particular intracellular environments, are reviewed.

Graphical abstract: Lanthanide-based tools for the investigation of cellular environments
From the themed collection: New molecules and materials from the f-block
Feature Article

Steric vs. electronic stereocontrol in syndio- or iso-selective ROP of functional chiral β-lactones mediated by achiral yttrium-bisphenolate complexes

Electronic vs. steric effects of ligand ortho-substituents in (bis)phenolate yttrium-based complexes for preparation of a large scope of stereoregular poly(3-hydroxyalkanoate)s.

Graphical abstract: Steric vs. electronic stereocontrol in syndio- or iso-selective ROP of functional chiral β-lactones mediated by achiral yttrium-bisphenolate complexes
From the themed collection: New molecules and materials from the f-block
Communication

Electrochemical oxidation of trivalent americium using a dipyrazinylpyridine modified ITO electrode

We present here the electrochemical oxidation of Am(III) to AmVO2+ and AmVIO22+ in pH 1 nitric acid using a mesoporous tin-doped indium oxide electrode modified with a covalently attached dipyrazinylpyridine ligand.

Graphical abstract: Electrochemical oxidation of trivalent americium using a dipyrazinylpyridine modified ITO electrode
From the themed collection: New molecules and materials from the f-block
Communication

Soft-donor dipicolinamide derivatives for selective actinide(III)/lanthanide(III) separation: the role of S- vs. O-donor sites

A dithiopicolinamide analog selectively extracts Am(III) over Eu(III) under acidic conditions.

Graphical abstract: Soft-donor dipicolinamide derivatives for selective actinide(iii)/lanthanide(iii) separation: the role of S- vs. O-donor sites
From the themed collection: New molecules and materials from the f-block
Communication

Moderate supercritical synthesis as a facile route to mixed-valent uranium(IV,V) and (V,VI) silicates

The synthesis of five new U(IV,V) and U(V,VI) silicates points toward moderate supercritical synthesis as a new route to the stabilization of mixed-valent uranium compounds.

Graphical abstract: Moderate supercritical synthesis as a facile route to mixed-valent uranium(iv,v) and (v,vi) silicates
From the themed collection: New molecules and materials from the f-block
Communication

Actinide-transition metal bonding in heterobimetallic uranium– and thorium–molybdenum paddlewheel complexes

Heterobimetallic An–Mo (An = U, Th) paddlewheel complexes featuring dative Mo → An bonds are reported.

Graphical abstract: Actinide-transition metal bonding in heterobimetallic uranium– and thorium–molybdenum paddlewheel complexes
From the themed collection: New molecules and materials from the f-block
Communication

Ca(II), Yb(II) and Tm(III) complexes with tri- and tetra-anions of 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene

Sandwich-like structures derived from organic polyanions and multi-centered cation assemblies.

Graphical abstract: Ca(ii), Yb(ii) and Tm(iii) complexes with tri- and tetra-anions of 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene
From the themed collection: New molecules and materials from the f-block
Communication

Single crystal growth and magnetic properties of the mixed valent Yb containing Zintl phase, Yb14MgSb11

Large crystals of Yb14MgSb11 prepared by Sn flux show the presence of Yb3+ making this compound a Zintl phase.

Graphical abstract: Single crystal growth and magnetic properties of the mixed valent Yb containing Zintl phase, Yb14MgSb11
From the themed collection: New molecules and materials from the f-block
Communication

Exploring the electronic structure and speciation of aqueous and colloidal Pu with high energy resolution XANES and computations

Pu L3 HR-XANES fingerprints loss of inversion symmetry: rising pre-edge (d,e), shorter A–B distance (d,e), split Pu d-DOS (e).

Graphical abstract: Exploring the electronic structure and speciation of aqueous and colloidal Pu with high energy resolution XANES and computations
From the themed collection: New molecules and materials from the f-block
Communication

Plutonium coordination and redox chemistry with the CyMe4-BTPhen polydentate N-donor extractant ligand

Complexation of Pu(IV) with the actinide extractant CyMe4-BTPhen (2,9-bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-1,2,4-benzotriazin-3-yl)-1,10-phenanthroline) was studied experimentally and by computational analysis.

Graphical abstract: Plutonium coordination and redox chemistry with the CyMe4-BTPhen polydentate N-donor extractant ligand
From the themed collection: New molecules and materials from the f-block
Communication

The electronic structure of f-element Prussian blue analogs determined by soft X-ray absorption spectroscopy

Isomorphous lanthanides and actinides Prussian blue analogs showing distinct optical and vibrational properties are studied using nitrogen K edge and iron K edge.

Graphical abstract: The electronic structure of f-element Prussian blue analogs determined by soft X-ray absorption spectroscopy
From the themed collection: New molecules and materials from the f-block
Communication

Organosoluble tetravalent actinide di- and trifluorides

Soluble molecular actinide(IV) fluorides can be prepared in high yield via redox or metathesis reactions of silver fluorides with actinide compounds containing ancillary iodide or fluorinated thiolate ligands.

Graphical abstract: Organosoluble tetravalent actinide di- and trifluorides
From the themed collection: New molecules and materials from the f-block
Communication

Plutonium chlorido nitrato complexes: ligand competition and computational metrics for assembly and bonding

Four novel Pu(IV) nitrato chloro complexes were crystallographically characterized and the Pu–ligand bond nature was delineated computationally.

Graphical abstract: Plutonium chlorido nitrato complexes: ligand competition and computational metrics for assembly and bonding
From the themed collection: New molecules and materials from the f-block
Communication

Stereo-selectivity switchable ROP of rac-β-butyrolactone initiated by salan-ligated rare-earth metal amide complexes: the key role of the substituents on ligand frameworks

A series of novel salan-ligated rare-earth metal amide complexes were prepared and employed as initiators for the ROP of rac-β-butyrolactone (rac-BBL).

Graphical abstract: Stereo-selectivity switchable ROP of rac-β-butyrolactone initiated by salan-ligated rare-earth metal amide complexes: the key role of the substituents on ligand frameworks
From the themed collection: New molecules and materials from the f-block
Communication

Polyethyleneimine methylenecarboxylate: a macromolecular DTPA analogue to chelate plutonium(IV)

Polyethyleneimine methylenecarboxylate (PEI-MC) is explored as a possible new class of macromolecular decorporation agents in case of plutonium contamination.

Graphical abstract: Polyethyleneimine methylenecarboxylate: a macromolecular DTPA analogue to chelate plutonium(iv)
From the themed collection: New molecules and materials from the f-block
Communication

Solid-state structural elucidation and electrochemical analysis of uranyl naphthylsalophen

The synthesis, characterization, and electrochemical properties of a napthylsalophen and its uranyl (UO22+) complex are described.

Graphical abstract: Solid-state structural elucidation and electrochemical analysis of uranyl naphthylsalophen
From the themed collection: New molecules and materials from the f-block
Open Access Communication

The semiquinone radical anion of 1,10-phenanthroline-5,6-dione: synthesis and rare earth coordination chemistry

The redox-active ligand as a route to heterobimetallic rare earth-transition metal compounds containing a semiquinone radical anion.

Graphical abstract: The semiquinone radical anion of 1,10-phenanthroline-5,6-dione: synthesis and rare earth coordination chemistry
From the themed collection: New molecules and materials from the f-block
Communication

Molecular hydrides of divalent ytterbium supported by a macrocyclic ligand: synthesis, structure and olefin hydrofunctionalization catalysis

Cationic ytterbium hydrides [(Me4TACD)2Yb2H(2+n)](2−n)+ (n = 0, 1) catalyzed the H2/D2 isotope exchange as well as hydrogenation and hydrosilylation of 1-hexene.

Graphical abstract: Molecular hydrides of divalent ytterbium supported by a macrocyclic ligand: synthesis, structure and olefin hydrofunctionalization catalysis
From the themed collection: New molecules and materials from the f-block
Communication

Post Hartree–Fock calculations of pnictogen–uranium bonding in EUF3 (E = N–Bi)

CASSCF and CASPT2 calculations are reported on EUF3 (E = N, P, As, Sb, Bi), emphasising the influence of the size of the active space on the E–U bond.

Graphical abstract: Post Hartree–Fock calculations of pnictogen–uranium bonding in EUF3 (E = N–Bi)
From the themed collection: New molecules and materials from the f-block
Communication

Catalytic regeneration of a Th–H bond from a Th–O bond through a mild and chemoselective carbonyl hydroboration

Organoactinide-mediated chemoselective hydroboration of aldehydes and ketones. The catalytic regeneration of a Th–H bond from a Th–OR bond was achieved via hydroboration with HBpin.

Graphical abstract: Catalytic regeneration of a Th–H bond from a Th–O bond through a mild and chemoselective carbonyl hydroboration
From the themed collection: New molecules and materials from the f-block
Communication

Two-electron oxidation of a homoleptic U(III) guanidinate complex by diphenyldiazomethane

Use of a new homoleptic U(III) tris-guanidinate system stabilizes the formation of the first U(V) hydrazido complex.

Graphical abstract: Two-electron oxidation of a homoleptic U(iii) guanidinate complex by diphenyldiazomethane
From the themed collection: New molecules and materials from the f-block
Communication

Towards understanding of lanthanide–transition metal bonding: investigations of the first Ce–Fe bonded complex

The syntheses, structural, and magnetic characterization of three new organometallic Ce complexes stabilized by PyCp22− (PyCp22− = [2,6-(CH2C5H3)2C5H3N]2−) are reported.

Graphical abstract: Towards understanding of lanthanide–transition metal bonding: investigations of the first Ce–Fe bonded complex
From the themed collection: New molecules and materials from the f-block
Communication

Impacts of oxo interactions within actinyl metal organic materials: highlight on thermal expansion behaviour

Interactions between H-donors and U(VI) and Np(V) oxo groups impact the thermal expansion properties of materials.

Graphical abstract: Impacts of oxo interactions within actinyl metal organic materials: highlight on thermal expansion behaviour
From the themed collection: New molecules and materials from the f-block
Communication

Reductive activation of neptunyl and plutonyl oxo species with a hydroxypyridinone chelating ligand

Neptunyl(VI) and plutonyl(VI) oxo-activation with reduction to tetravalent hydroxides was investigated in gas and condensed phases, and by density functional theory.

Graphical abstract: Reductive activation of neptunyl and plutonyl oxo species with a hydroxypyridinone chelating ligand
From the themed collection: New molecules and materials from the f-block
Communication

Spiral Eu(III) coordination polymers with circularly polarized luminescence

A spiral-type chiral Eu(III) coordination polymer showed strong luminescence, effective CD and CPL properties compared with a mono-nuclear chiral Eu(III) complex in the solid state.

Graphical abstract: Spiral Eu(iii) coordination polymers with circularly polarized luminescence
From the themed collection: New molecules and materials from the f-block
Communication

Revisiting complexation thermodynamics of transplutonium elements up to einsteinium

In contrast with previous literature, this report notes einsteium's chemistry is a continuation of the earlier actinide series.

Graphical abstract: Revisiting complexation thermodynamics of transplutonium elements up to einsteinium
From the themed collection: New molecules and materials from the f-block
Communication

Structure and properties of [(4,6-tBu2C6H2O)2Se]2An(THF)2, An = U, Np, and their reaction with p-benzoquinone

The synthesis and characterization of U(IV) and Np(IV) selenium bis(phenolate) complexes are reported.

Graphical abstract: Structure and properties of [(4,6-tBu2C6H2O)2Se]2An(THF)2, An = U, Np, and their reaction with p-benzoquinone
From the themed collection: New molecules and materials from the f-block
Communication

Photochemical and electrochemical hydrogen evolution reactivity of lanthanide-functionalized polyoxotungstates

The first example of molecular lanthanide tungstate clusters for photochemical and electrochemical hydrogen evolution catalysis is reported.

Graphical abstract: Photochemical and electrochemical hydrogen evolution reactivity of lanthanide-functionalized polyoxotungstates
From the themed collection: New molecules and materials from the f-block
Communication

Modelling uranyl chemistry in liquid ammonia from density functional theory

We developed a computationally-efficient protocol based on Density Functional Theory (DFT) and a continuum solvation model (CSM) to predict reaction free energies of complexation reactions of uranyl in liquid ammonia.

Graphical abstract: Modelling uranyl chemistry in liquid ammonia from density functional theory
From the themed collection: New molecules and materials from the f-block
Communication

The “Wanderlust” of Me3Si groups in rare-earth triple-decker complexes: a combined experimental and computational study

The migration of Me3Si groups (“Wanderlust”) in rare-earth triple-decker sandwich complexes of the type Ln2(COT′′)3 (COT′′ = bis(trimethylsilyl)cyclooctatetraenyl) has been elucidated by a combined experimental and computational study.

Graphical abstract: The “Wanderlust” of Me3Si groups in rare-earth triple-decker complexes: a combined experimental and computational study
From the themed collection: New molecules and materials from the f-block
Communication

Synthesis of uranium-in-cryptand complexes

Uranium-in-cryptand complexes can be readily synthesized by reacting UI3 with 2.2.2-cryptand.

Graphical abstract: Synthesis of uranium-in-cryptand complexes
From the themed collection: New molecules and materials from the f-block
Communication

A tetranuclear samarium(II) inverse sandwich from direct reduction of toluene by a samarium(II) siloxide

The dinuclear SmII complex [Sm2L4(dme)] (L = OSi(OtBu)3) reacts slowly with toluene, resulting in the isolation of the triple decker arene-bridged SmII complex [{Sm2L3}2(μ-η66-C7H8)] in 44% yield. This reactivity provides the first example of an unambiguous arene reduction by an isolated SmII species.

Graphical abstract: A tetranuclear samarium(ii) inverse sandwich from direct reduction of toluene by a samarium(ii) siloxide
From the themed collection: New molecules and materials from the f-block
Communication

A molecular basis to rare earth separations for recycling: tuning the TriNOx ligand properties for improved performance

A methoxy-substituted tripodal hydroxylamine ligand, H3TriNOxOMe, was synthesized and coordinated to rare earth cations for separation purposes.

Graphical abstract: A molecular basis to rare earth separations for recycling: tuning the TriNOx ligand properties for improved performance
From the themed collection: New molecules and materials from the f-block
Communication

Exploring the intramolecular catalysis of the proton exchange process to modulate the relaxivity of Gd(III)-complexes of HP-DO3A-like ligands

The GdIII complex of Ph-HP-DO3A shows the highest contribution to the relaxivity by the intramolecular proton exchange of the –OH group.

Graphical abstract: Exploring the intramolecular catalysis of the proton exchange process to modulate the relaxivity of Gd(iii)-complexes of HP-DO3A-like ligands
From the themed collection: New molecules and materials from the f-block
Open Access Communication

{Np38} clusters: the missing link in the largest poly-oxo cluster series of tetravalent actinides

The poly-oxo clusters of neptunium, {Np38}, fill the gap in the largest poly-oxo cluster series of tetravalent actinides.

Graphical abstract: {Np38} clusters: the missing link in the largest poly-oxo cluster series of tetravalent actinides
From the themed collection: New molecules and materials from the f-block
Communication

Square supramolecular assemblies of uranyl complexes in organic solvents

Uranyl, ligand and solvent interactions lead to unique supramolecular assembly.

Graphical abstract: Square supramolecular assemblies of uranyl complexes in organic solvents
From the themed collection: New molecules and materials from the f-block
Communication

Trends in the valence band electronic structures of mixed uranium oxides

The valence band electronic structures of mixed uranium oxides (UO2, U4O9, U3O7, U3O8, and β-UO3) have been studied using the resonant inelastic X-ray scattering (RIXS) technique at the U M5 edge and computational methods.

Graphical abstract: Trends in the valence band electronic structures of mixed uranium oxides
From the themed collection: New molecules and materials from the f-block
Open Access Communication

Elucidation of the inverse trans influence in uranyl and its imido and carbene analogues via quantum chemical simulation

The inverse trans influence is quantified in uranyl and its analogues via analysis of quantum chemically-derived electron density distributions.

Graphical abstract: Elucidation of the inverse trans influence in uranyl and its imido and carbene analogues via quantum chemical simulation
From the themed collection: New molecules and materials from the f-block
Communication

Uranyl dication mediated photoswitching of a calix[4]pyrrole-based metal coordination cage

A set of self-assembled tri- and tetrapodal metal coordination cage structures (cage-1 and cage-2, respectively) constructed from the uranyl dication (UO22+) and a dibenzoic acid functionalised cis-calix[4]pyrrole (1) are described.

Graphical abstract: Uranyl dication mediated photoswitching of a calix[4]pyrrole-based metal coordination cage
From the themed collection: New molecules and materials from the f-block
Communication

Terbocenium: completing a heavy lanthanide metallocenium cation family with an alternative anion abstraction strategy

A series of lanthanide metallocenium cations [Ln(Cpttt)2]+ (Ln = Y, Gd, Dy, Ho, Er, Tm, Yb, Lu; Cpttt = C5H2tBu3-1,2,4) were recently prepared, but curiously the Tb analogue was elusive. Here we access [Tb(Cpttt)2]+via an alternative strategy, completing the heavy [Ln(Cpttt)2]+ family.

Graphical abstract: Terbocenium: completing a heavy lanthanide metallocenium cation family with an alternative anion abstraction strategy
From the themed collection: New molecules and materials from the f-block
Communication

Activation of carbon suboxide (C3O2) by U(III) to form a cyclobutane-1,3-dione ring

[U(η5-C5H4SiMe3)3] reductively couples three C3O2 molecules to form a tetranuclear complex with a central cyclobutane-1,3-dione ring, via an intermediate bridging ketene complex.

Graphical abstract: Activation of carbon suboxide (C3O2) by U(iii) to form a cyclobutane-1,3-dione ring
From the themed collection: New molecules and materials from the f-block
Communication

Synthesis of homometallic divalent lanthanide organoimides from benzyl complexes

Double protonolysis of [Ln(CH2Ph)2]n (Ln = Eu and Yb) with 2,6-diisopropylaniline gives efficient access to [(thf)Ln(μ3-NDipp)]4 featuring a heterocubane structure.

Graphical abstract: Synthesis of homometallic divalent lanthanide organoimides from benzyl complexes
From the themed collection: New molecules and materials from the f-block
Communication

Schiff-base coordination complexes with plutonium(IV) and cerium(IV)

The synthesis and characterization of a Pu(IV) salen complex reveals the stabilization of the +4 oxidation state with respect to that observed with Ce(IV).

Graphical abstract: Schiff-base coordination complexes with plutonium(iv) and cerium(iv)
From the themed collection: New molecules and materials from the f-block
Communication

Yet again, new compounds found in systems with known binary phase diagrams. Synthesis, crystal and electronic structure of Nd3Bi7 and Sm3Bi7

Reported, for the very first time, are the synthesis and structures of two new compounds, discovered in well-studied binary phase diagrams.

Graphical abstract: Yet again, new compounds found in systems with known binary phase diagrams. Synthesis, crystal and electronic structure of Nd3Bi7 and Sm3Bi7
From the themed collection: New molecules and materials from the f-block
Communication

Single-molecule magnet properties of a monometallic dysprosium pentalene complex

The pentalene-ligated dysprosium complex [(η8-Pn)Dy(Cp*)] (1Dy) (Pn = [1,4-(iPr3Si)2C8H4]2−) and its magnetically dilute analogue are single-molecule magnets, with energy barriers of 245 cm−1.

Graphical abstract: Single-molecule magnet properties of a monometallic dysprosium pentalene complex
From the themed collection: New molecules and materials from the f-block
Communication

Synthesis and structural characterization of the first neptunium based metal–organic frameworks incorporating {Np6O8} hexanuclear clusters

The synthesis of the first transuranium Metal–Organic Frameworks (TRU-MOFs) is reported here.

Graphical abstract: Synthesis and structural characterization of the first neptunium based metal–organic frameworks incorporating {Np6O8} hexanuclear clusters
From the themed collection: New molecules and materials from the f-block
Communication

Homoleptic uranium and lanthanide phosphinodiboranates

The synthesis and structures of a new class of homoleptic f-metal borohydride complexes (phosphinodiboranates) are described with U, Nd, and Er.

Graphical abstract: Homoleptic uranium and lanthanide phosphinodiboranates
From the themed collection: New molecules and materials from the f-block
Open Access Communication

Double uranium oxo cations derived from uranyl by borane or silane reduction

A new type of double uranium oxo cation [O–U–O–U–O]4+ is prepared by selective oxygen-atom abstraction from macrocyclic uranyl complexes using either boranes or silanes.

Graphical abstract: Double uranium oxo cations derived from uranyl by borane or silane reduction
48 items

About this collection

This web themed issue highlights the breadth of ongoing research into the fundamental structure and bonding, and diversity of application of compounds of the f-block. Contributions cover complementary but diverse approaches and rare earth chemistry, ranging from computation and solid-state studies to synchrotron studies.
The collection is guest edited by Professor Polly Arnold, OBE, FRSE, FRSC (University of Edinburgh) and Professor Sarah Stoll (Georgetown University).
Articles in this web themed issue will be added below as soon as possible after they are published. Please return to this page frequently to see the collection grow.

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