RESUMEN

Recent advances enabled the discovery of heterometallic molecules for many metals: main group, d-block, lanthanides, and some actinides (U, Th). These complexes have at least two different metals joined by bridging ligands or by direct metal-metal bonding interactions. They are attractive because they can enable chemical cooperativity between metals from different parts of the periodic table. Some heterometallics provide access to unique reactivity and others exhibit physical properties that cannot be accessed by homometallic species. We envisioned that transuranic heterometallics might similarly enable new transuranic chemistry, though synthetic routes to such compounds have yet to be developed. Reported here is the first synthesis of a molecular transuranic complex that contains plutonium (Pu) and cobalt (Co). Our analyses of PuCl3{CoCp[OP(OEt)2]3} showed Pu(iv) and Co(iii) were present and suggested that the Pu(iv) oxidation state was stabilized by the electron donating phosphite ligands. This synthetic method - and the demonstration that Pu(iv) can be stabilized in a heterobimetallic molecular setting - provides a foundation for further exploration of transuranic multimetallic chemistry.

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The nature of charge degrees-of-freedom distinguishes scenarios for interpreting the character of a second order magnetic transition at zero temperature, that is, a magnetic quantum critical point (QCP). Heavy-fermion systems are prototypes of this paradigm, and in those, the relevant question is where, relative to a magnetic QCP, does the Kondo effect delocalize their f-electron degrees-of-freedom. Herein, we use pressure-dependent Hall measurements to identify a finite-temperature scale Eloc that signals a crossover from f-localized to f-delocalized character. As a function of pressure, Eloc(P) extrapolates smoothly to zero temperature at the antiferromagnetic QCP of CeRhIn5 where its Fermi surface reconstructs, hallmarks of Kondo-breakdown criticality that generates critical magnetic and charge fluctuations. In 4.4% Sn-doped CeRhIn5, however, Eloc(P) extrapolates into its magnetically ordered phase and is decoupled from the pressure-induced magnetic QCP, which implies a spin-density-wave (SDW) type of criticality that produces only critical fluctuations of the SDW order parameter. Our results demonstrate the importance of experimentally determining Eloc to characterize quantum criticality and the associated consequences for understanding the pairing mechanism of superconductivity that reaches a maximum Tc in both materials at their respective magnetic QCP.

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We report point-contact spectroscopy measurements on heavy fermion cousins CeCoIn5, Ce2PdIn8and Ce3PdIn11to systematically study the hybridization betweenfand conduction electrons. Below a temperatureT*, the spectrum of each compound exhibits an evolving Fano-like conductance shape, superimposed on a sloping background, that suggests the development of hybridization between localfand itinerant conduction electrons in the coherent heavy fermion state belowT*. We present a quantitative analysis of the conductance curves with a two-channel model to compare the tunneling process between normal metallic silver particles in our soft point-contact and heavy-fermion single crystals CeCoIn5, Ce2PdIn8and Ce3PdIn11.

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Low-dimensional electronic systems with confined electronic wave functions have attracted interest due to their propensity toward novel quantum phases and their use in wide range of nanotechnologies. The newly discovered chalcogenide Nb2PdS5 possesses a quasi-one-dimensional electronic structure and becomes superconducting. Here, we report spectroscopic evidence for two-band superconductivity, where soft point-contact spectroscopic measurements in the superconducting (SC) state reveal Andreev reflection in the differential conductance G. Multiple peaks in G are observed at 1.8 K and explained by the two-band Blonder-Tinkham-Klapwijk model with two gaps Δ1 = 0.61 meV and Δ2 = 1.20 meV. The progressive evolution of G with temperature and magnetic field corroborates the multiple nature of the SC gaps.

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We report on an optical technique for measuring thermal expansion and magnetostriction at cryogenic temperatures and under applied hydrostatic pressures of 2.0 GPa. Optical fiber Bragg gratings inside a clamp-type pressure chamber are used to measure the strain in a millimeter-sized sample of CeRhIn5. We describe the simultaneous measurement of two Bragg gratings in a single optical fiber using an optical sensing instrument capable of resolving changes in length [dL/L = (L- L0)/L0] on the order of 10-7. Our results demonstrate the possibility of performing high-resolution thermal expansion measurements under hydrostatic pressure, a capability previously hindered by the small working volumes typical of pressure cells.

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Resonant x-ray scattering (RXS) has recently become an increasingly important tool for the study of ordering phenomena in correlated electron systems. Yet, the interpretation of RXS experiments remains theoretically challenging because of the complexity of the RXS cross section. Central to this debate is the recent proposal that impurity-induced Friedel oscillations, akin to quasi-particle interference signals observed with a scanning tunneling microscope (STM), can lead to scattering peaks in RXS experiments. The possibility that quasi-particle properties can be probed in RXS measurements opens up a new avenue to study the bulk band structure of materials with the orbital and element selectivity provided by RXS. We test these ideas by combining RXS and STM measurements of the heavy fermion compound CeMIn5 (M = Co, Rh). Temperature- and doping-dependent RXS measurements at the Ce-M4 edge show a broad scattering enhancement that correlates with the appearance of heavy f-electron bands in these compounds. The scattering enhancement is consistent with the measured quasi-particle interference signal in the STM measurements, indicating that the quasi-particle interference can be probed through the momentum distribution of RXS signals. Overall, our experiments demonstrate new opportunities for studies of correlated electronic systems using the RXS technique.

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Black TiO2 nanoparticles with a crystalline core and amorphous-shell structure exhibit superior optoelectronic properties in comparison with pristine TiO2. The fundamental mechanisms underlying these enhancements, however, remain unclear, largely due to the inherent complexities and limitations of powder materials. Here, we fabricate TiO2 homojunction films consisting of an oxygen-deficient amorphous layer on top of a highly crystalline layer, to simulate the structural/functional configuration of black TiO2 nanoparticles. Metallic conduction is achieved at the crystalline-amorphous homointerface via electronic interface reconstruction, which we show to be the main reason for the enhanced electron transport of black TiO2. This work not only achieves an unprecedented understanding of black TiO2 but also provides a new perspective for investigating carrier generation and transport behavior at oxide interfaces, which are of tremendous fundamental and technological interest.

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The synthesis, electronic structure, and characterization via single-crystal X-ray diffraction, nuclear magnetic resonance (NMR) spectroscopy, and magnetic susceptibility of (Me4N)2PuCl6 are reported. NMR measurements were performed to both search for the direct (239)Pu resonance and to obtain local magnetic and electronic information at the Cl site through (35)Cl and (37)Cl spectra. No signature of (239)Pu NMR was observed. The temperature dependence of the Cl spectra was simulated by diagonalizing the Zeeman and quadrupolar Hamiltonians for (35)Cl, (37)Cl, and (14)N isotopes. Electronic structure calculations predict a magnetic Γ5 triplet ground state of Pu(IV) in the crystalline electric field of the undistorted PuCl6 octahedron. A tetragonal distortion would result in a very small splitting (∼20 cm(-1)) of the triplet ground state into a nonmagnetic singlet and a doublet state. The Cl shifts have an inflection point at T ≈ 15 K, differing from the bulk susceptibility, indicating a nonmagnetic crystal field ground state. The Cl spin-lattice relaxation time is constant to T = 15 K, below which it rapidly increases, also supporting the nonmagnetic crystal field ground state.

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A central issue in material science is to obtain understanding of the electronic correlations that control complex materials. Such electronic correlations frequently arise because of the competition of localized and itinerant electronic degrees of freedom. Although the respective limits of well-localized or entirely itinerant ground states are well understood, the intermediate regime that controls the functional properties of complex materials continues to challenge theoretical understanding. We have used neutron spectroscopy to investigate plutonium, which is a prototypical material at the brink between bonding and nonbonding configurations. Our study reveals that the ground state of plutonium is governed by valence fluctuations, that is, a quantum mechanical superposition of localized and itinerant electronic configurations as recently predicted by dynamical mean field theory. Our results not only resolve the long-standing controversy between experiment and theory on plutonium's magnetism but also suggest an improved understanding of the effects of such electronic dichotomy in complex materials.

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Rare-earth metal germanides with the general formula RE(4)Ge(7) (RE = La, Ce, Pr, Nd, Sm) have been synthesized using the In-flux technique. Their structures have been established from single-crystal and powder X-ray diffraction, and the structural elucidation has been aided by electron diffraction. These compounds represent superstructures of the α-ThSi(2) structure type through the long- and/or short-range vacancy ordering. RE(4)Ge(7) (RE = Pr, Nd, Sm) appear to be commensurately modulated 4-fold superstructure of REGe(2-x) (x = 1/4), while coexistence of commensurate and incommensurate modulation is revealed in the La- and Ce-analogues. These results shed more light on the structural evolution of the REGe(2-x) phases as function of the vacancy concentration and nature of the rare-earth metal. Measurements of the magnetic susceptibilities on well-characterized single-crystals show ferromagnetic, antiferromagnetic, and even spin-glass-like behaviors. Mean-field theory is used to evaluate the correlations between structural and magnetic property data. Measurements on the electrical resistivities and the heat capacities are also presented and discussed.

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The first designed molecular catalyst for water oxidation is the "blue dimer", cis,cis-[(bpy)(2)(H(2)O)Ru(III)ORu(III)(OH(2))(bpy)(2)](4+). Although there is experimental evidence for extensive electronic coupling across the µ-oxo bridge, results of earlier DFT and CASSCF calculations provide a model with magnetic interactions of weak to moderately coupled Ru(III) ions across the µ-oxo bridge. We present the results of a comprehensive experimental investigation, combined with DFT calculations. The experiments demonstrate both that there is strong electronic coupling in the blue dimer and that its effects are profound. Experimental evidence has been obtained from molecular structures and key bond distances by XRD, electrochemically measured comproportionation constants for mixed-valence equilibria, temperature-dependent magnetism, chemical properties (solvent exchange, redox potentials, and pK(a) values), XPS binding energies, analysis of excitation-dependent resonance Raman profiles, and DFT analysis of electronic absorption spectra. The spectrum can be assigned based on a singlet ground state with specific hydrogen-bonding interactions with solvent molecules included. The results are in good agreement with available experimental data. The DFT analysis provides assignments for characteristic absorption bands in the near-IR and visible regions. Bridge-based dπ → dπ* and interconfiguration transitions at Ru(III) appear in the near-IR and MLCT and LMCT transitions in the visible. Reasonable values are also provided by DFT analysis for experimentally observed bond distances and redox potentials. The observed temperature-dependent magnetism of the blue dimer is consistent with a delocalized, diamagnetic singlet state (dπ(1)*)(2) with a low-lying, paramagnetic triplet state (dπ(1)*)(1)(dπ(2)*)(1). Systematic structural-magnetic-IR correlations are observed between ν(sym)(RuORu) and ν(asym)(RuORu) vibrational energies and magnetic properties in a series of ruthenium-based, µ-oxo-bridged complexes. Consistent with the DFT electronic structure model, bending along the Ru-O-Ru axis arises from a Jahn-Teller distortion with ∠Ru-O-Ru dictated by the distortion and electron-electron repulsion.

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Understanding how individual cells behave inside living systems will help enable new diagnostic tools and cellular therapies. Superparamagnetic iron oxide particles can be used to label cells and theranostic capsules for noninvasive tracking using MRI. Contrast changes from superparamagnetic iron oxide are often subtle relative to intrinsic sources of contrast, presenting a detection challenge. Here, we describe a versatile postprocessing method, called Phase map cross-correlation Detection and Quantification (PDQ), that automatically identifies localized deposits of superparamagnetic iron oxide, estimating their volume magnetic susceptibility and magnetic moment. To demonstrate applicability, PDQ was used to detect and characterize superparamagnetic iron oxide-labeled magnetocapsules implanted in porcine liver and suspended in agarose gel. PDQ was also applied to mouse brains infiltrated by MPIO-labeled macrophages following traumatic brain injury; longitudinal, in vivo studies tracked individual MPIO clusters over 3 days, and tracked clusters were corroborated in ex vivo brain scans. Additionally, we applied PDQ to rat hearts infiltrated by MPIO-labeled macrophages in a transplant model of organ rejection. PDQ magnetic measurements were signal-to-noise ratio invariant for images with signal-to-noise ratio > 11. PDQ can be used with conventional gradient-echo pulse sequences, requiring no extra scan time. The method is useful for visualizing biodistribution of cells and theranostic magnetocapsules and for measuring their relative iron content.

Asunto(s)

RESUMEN

We report here an efficient noncovalent chemical route to dense and uniform assembly of magnetic nanoparticles onto multi-walled carbon nanotubes within a single-layer configuration. While preserving the electrical conduction behavior of the nanotube network itself, the resulting carbon nanotube derivatives exhibit a distinct superparamagnetism, and can be magnetically manipulated via a quick and reversible mode.

Asunto(s)

RESUMEN

A comparative examination of the electronic interactions across a series of trimetallic actinide and mixed lanthanide-actinide and lanthanum-actinide complexes is presented. Using reduced, radical terpyridyl ligands as conduits in a bridging framework to promote intramolecular metal-metal communication, studies containing structural, electrochemical, and X-ray absorption spectroscopy are reported for (C(5)Me(5))(2)An[-N horizontal lineC(Bn)(tpy-M{C(5)Me(4)R}(2))](2) (where An = Th(IV), U(IV); Bn = CH(2)C(6)H(5); M = La(III), Sm(III), Yb(III), U(III); R = H, Me, Et) to reveal effects dependent on the identities of the metal ions and R-groups. The electrochemical results show differences in redox energetics at the peripheral "M" site between complexes and significant wave splitting of the metal- and ligand-based processes indicating substantial electronic interactions between multiple redox sites across the actinide-containing bridge. Most striking is the appearance of strong electronic coupling for the trimetallic Yb(III)-U(IV)-Yb(III), Sm(III)-U(IV)-Sm(III), and La(III)-U(IV)-La(III) complexes, [8](-), [9b](-), and [10b](-), respectively, whose calculated comproportionation constant K(c) is slightly larger than that reported for the benchmark Creutz-Taube ion. X-ray absorption studies for monometallic metallocene complexes of U(III), U(IV), and U(V) reveal small but detectable energy differences in the "white-line" feature of the uranium L(III)-edges consistent with these variations in nominal oxidation state. The sum of these data provides evidence of 5f/6d-orbital participation in bonding and electronic delocalization in these multimetallic f-element complexes. An improved, high-yielding synthesis of 4'-cyano-2,2':6',2''-terpyridine is also reported.

RESUMEN

Actinide complexes of the redox-active ligand (dpp-BIAN)(2-) (dpp-BIAN = 1,2-bis(2,6-diisopropylphenylimino)acenaphthylene), U(dpp-BIAN)(2) (1), U(dpp-BIAN)(2)(THF) (1-THF), and Th(dpp-BIAN)(2)(THF) (2-THF), have been prepared. Solid-state magnetic and single-crystal X-ray data for complex 1 indicate a ground-state U(IV)-pi*(4) configuration, whereas a (dpp-BIAN)(2-)-to-uranium electron transfer occurs for 1-THF, resulting in a U(III)-pi*(3) ground configuration. The solid-state magnetic data also indicate that interconversion between the two forms of the complex is possible, limited only by the ability of tetrahydrofuran (THF) vapor to penetrate the solid upon cooling of the sample. In contrast to those in the solid state, spectroscopic data acquired in THF indicate only the presence of the U(IV)-pi*(4) form for 1-THF in solution, evidenced by electronic absorption spectra and by measurement of the solution magnetic moment in THF-d(8) using the Evans method. Also reported is the electrochemistry of the complexes collected in CH(2)Cl(2), CF(3)C(6)H(5), and THF. As expected from the solution spectroscopic data, only small differences are observed in half-wave potentials of ligand-based processes in the presence of THF, consistent with the solution U(IV)-pi*(4) configuration of the complexes in all cases. Density functional theory calculations were undertaken for complexes 1 and 1-THF to determine if intrinsic energetic or structural factors underlie the observed charge-transfer process. While the calculated optimized geometries agree well with experimental results, it was not possible to arrive at a convergent solution for 1-THF in the U(III)-pi*(3) configuration. However, perturbations in the orbital energies in 1 versus 1-THF for the U(IV)-pi*(4) configuration do point to a diminished highest occupied molecular orbital-lowest unoccupied molecular orbital energy gap in 1-THF, consistent with the solid-state magnetic data. These results represent the first example of a stable and well-defined, reversible intramolecular electron transfer in an actinide complex with redox-active ligands.

RESUMEN

A series of magnesium-substituted rare-earth metal germanides with a general formula RE(5-x)Mg(x)Ge(4) (x approximately = 1.0-2.3; RE = Gd-Tm, Lu, Y) have been synthesized by high-temperature reactions and structurally characterized by single-crystal X-ray diffraction. These compounds crystallize with the common Gd(5)Si(4) type structure in the orthorhombic space group Pnma (No. 62; Z = 4; Pearson's code oP36) and do not appear to undergo temperature-induced crystallographic phase transitions down to 120 K. Replacing rare-earth metal atoms with Mg, up to nearly 45% at., reduces the valence electron count and is clearly expressed in the subtle changes of the Ge-Ge and metal-metal bonding. Magnetization measurements as a function of the temperature and the applied field reveal complex magnetic structures at cryogenic temperatures and Curie-Weiss paramagnetic behavior at higher temperatures. The observed local moment magnetism is consistent with RE(3+) ground states in all cases. In the magnetically ordered phases, the magnetization cannot reach saturation in fields up to 50 kOe. The structural trends across the series and the variations of the magnetic properties as a function of the Mg content are also discussed.

RESUMEN

Communication is important: The dimeric bis(imido) uranium complex [{U(NtBu)(2)(I)(tBu(2)bpy)}(2)] (see picture; U green, N blue, I red) has cation-cation interactions between [U(NR)(2)](+) ions. This f(1)-f(1) system also displays f orbital communication between uranium(V) centers at low temperatures, and can be oxidized to generate uranium(VI) bis(imido) complexes.

RESUMEN

A series of organometallic pentavalent uranium complexes of the general formula (C(5)Me(5))(2)U(=N-2,6-(i)Pr(2)-C(6)H(3))(Y) (Y = monoanionic, non-halide ligand) have been prepared using a variety of routes. Utilizing the direct oxidation of (C(5)Me(5))(2)U(=N-2,6-(i)Pr(2)-C(6)H(3))(THF) (2) with the appropriate copper(I) salt yielded the triflate (Y = OTf (OSO(2)CF(3)), 11), thiolate (Y = SPh, 12), and acetylide (Y = C[triple bond]CPh, 13) complexes, while a salt metathesis route between the U(V)-imido (C(5)Me(5))(2)U(=N-2,6-(i)Pr(2)-C(6)H(3))(I) (10) and various alkali salts gave the diphenylamide (Y = NPh(2), 14), aryloxide (Y = OPh, 15), alkyl (Y = Me, 16), and aryl (Y = Ph, 17) complexes. Paired with 13, the isolation of 16 and 17 shows that U(V) can support the full range of carbon anions (sp, sp(2), and sp(3)), and these are, to the best of our knowledge, the first examples of pentavalent uranium complexes with anionic carbon moieties other than carbocyclic (C(5)R(5), C(7)H(7), C(8)H(8)) ligands. Finally, both protonolysis and insertion pathways afforded the U(V)-imido ketimide complex (C(5)Me(5))(2)U(=N-2,6-(i)Pr(2)-C(6)H(3))(N=CPh(2)) (18). The complexes have been isolated in good yield and characterized using various combinations of (1)H NMR spectroscopy, elemental analysis, mass spectrometry, single crystal X-ray diffraction, cyclic voltammetry, UV-visible-NIR absorption spectroscopy, and magnetic susceptibility measurements. All (C(5)Me(5))(2)U(=N-Ar)(X) (X = F, Cl, Br, I) and (C(5)Me(5))(2)U(=N-Ar)(Y) complexes exhibit U(VI)/U(V) and U(V)/U(IV) redox couples by voltammetry. The potential separation between these couples remains essentially constant at approximately 1.50 V, but both processes shift in tandem in potential by approximately 700 mV across the series of X/Y ligands. No significant differences between mu(eff) values or temperature dependencies in the magnetic susceptibility were observed for these complexes regardless of the identity of the ancillary X/Y ligand. However, an excellent linear correlation was observed between the chemical shift values of C(5)Me(5) ligand protons in the (1)H NMR spectra and the oxidation potentials of (C(5)Me(5))(2)U(=N-2,6-(i)Pr(2)-C(6)H(3))(X/Y), suggesting that there is a common origin, overall sigma-/pi-donation from the ancillary X/Y ligand to the metal, contributing to both observables. Combined, these data confer the following trend in increasing sigma/pi-donating ability of the X/Y ligand to the U(V) metal center: OTf < I < Br < Cl < SPh < C[triple bond]CPh < F < [OPh approximately Me approximately Ph] << NPh(2) < N=CPh(2). These (C(5)Me(5))(2)U(=N-2,6-(i)Pr(2)-C(6)H(3))(X/Y) complexes also show distinct hallmarks of a covalent bonding interaction between the metal and the imide ligand that is modulated to varying degrees by the interaction between the X/Y ancillary ligand and the U(V) metal center. These signatures of covalency include stabilization of multiple metal oxidations states [U(VI), U(V), and U(IV)] and enhanced intensities in the intraconfiguration (f-f) transitions. Of particular note in this regard is the more than 20-fold enhancement in the f-f intensities observed for Y = C[triple bond]CPh and N=CPh(2), which is a clear reflection of the covalent metal-ligand bonding interactions sustained by the acetylide and ketimide ligands in these pentavalent systems.

RESUMEN

Reaction of two equivalents of [(C5Me4Et)2U(CH3)(Cl)] (6) or [(C5Me5)2Th(CH3)(Br)] (7) with 1,4-dicyanobenzene leads to the formation of the novel 1,4-phenylenediketimide-bridged bimetallic organoactinide complexes [((C5Me4Et)2(Cl)U)(2)(mu-(N=C(CH3)-C6H4-(CH3)C=N))] (8) and [((C5Me5)2(Br)Th)2(mu-(N=C(CH3)-C6H4- (CH3)C==N))] (9), respectively. These complexes were structurally characterized by single-crystal X-ray diffraction and NMR spectroscopy. Metal-metal interactions in these isovalent bimetallic systems were assessed by means of cyclic voltammetry, UV-visible/NIR absorption spectroscopy, and variable-temperature magnetic susceptibility. Although evidence for magnetic coupling between metal centers in the bimetallic U IV/U IV (5f2-5f2) complex is ambiguous, the complex displays appreciable electronic communication between the metal centers through the pi system of the dianionic diketimide bridging ligand, as judged by voltammetry. The transition intensities of the f-f bands for the bimetallic U IV/U IV system decrease substantially compared to the related monometallic ketimide chloride complex, [(C5Me5)2U(Cl)(-N=C(CH3)-(3,4,5-F(3)-C6H2))] (11). Also reported herein are new synthetic routes to the actinide starting materials [(C5Me4Et)(2)U(CH3)(Cl)] (6) and [(C5Me5)2Th(CH3)(Br)] (7) in addition to the syntheses and structures of the monometallic uranium complexes [(C5Me4Et)2UCl2] (3), [(C5Me4Et)2U(CH3)2] (4), [(C5Me4Et)2U(-N==C(CH3)-C6H4-C==N)2] (10), and 11.