Molecular nitrogen (N) is cheap and widely available, but its unreactive nature is a challenge when attempting to functionalize it under mild conditions with other widely available substrates (such as carbon monoxide, CO) to produce value-added compounds. Biological N fixation can do this, but the industrial Haber-Bosch process for ammonia production operates under harsh conditions (450 degrees Celsius and 300 bar), even though both processes are thought to involve multimetallic catalytic sites. And although molecular complexes capable of binding and even reducing N under mild conditions are known, with co-operativity between metal centres considered crucial for the N reduction step, the multimetallic species involved are usually not well defined, and further transformation of N-binding complexes to achieve N-H or N-C bond formation is rare. Haber noted, before an iron-based catalyst was adopted for the industrial Haber-Bosch process, that uranium and uranium nitride materials are very effective heterogeneous catalysts for ammonia production from N. However, few examples of uranium complexes binding N are known, and soluble uranium complexes capable of transforming N into ammonia or organonitrogen compounds have not yet been identified. Here we report the four-electron reduction of N under ambient conditions by a fully characterized complex with two U ions and three K centres held together by a nitride group and a flexible metalloligand framework. The addition of H and/or protons, or CO to the resulting complex results in the complete cleavage of N with concomitant N functionalization through N-H or N-C bond-forming reactions. These observations establish that a molecular uranium complex can promote the stoichiometric transformation of N into NH or cyanate, and that a flexible, electron-rich, multimetallic, nitride-bridged core unit is a promising starting point for the design of molecular complexes capable of cleaving and functionalizing N under mild conditions.
Uniquely in Cu 2 OSeO 3 , the Skyrmions, which are topologically protected magnetic spin vortexlike objects, display a magnetoelectric coupling and can be manipulated by externally applied electric (E) fields. Here, we explore the E-field coupling to the magnetoelectric Skyrmion lattice phase, and study the response using neutron scattering. Giant E-field induced rotations of the Skyrmion lattice are achieved that span a range of ∼25°. Supporting calculations show that an E-field-induced Skyrmion distortion lies behind the lattice rotation. Overall, we present a new approach to Skyrmion control that makes no use of spin-transfer torques due to currents of either electrons or magnons. [12,13]. All have the chiral-cubic space group P2 1 3, a weak magnetocrystalline anisotropy, and common phase diagrams with a helimagnetic ground state. Despite these similarities, the diverse transport properties lead to material specific mechanisms for Skyrmion manipulation and the associated dynamics. In the well-studied itinerant compounds, spin-transfer torques (STTs) exerted by the conduction electrons of an ultralow current density, j ≲ 10 6 A·m −2 drive the Skyrmion motion [5,[14][15][16][17][18][19]. More generally, in both MnSi and insulating Cu 2 OSeO 3 , Skyrmion lattice (SKL) rotations are observed to be driven by STTs exerted by the magnon currents induced by a thermal gradient [20]. Even though electric currents and thermal gradients have been established to generate Skyrmion motion, it remains vital to find new control mechanisms which may lead to further efficient Skyrmion-based functionalities.In the insulating SKL host compounds, the chiral lattice promotes a magnetoelectric (ME) coupling between electric (E) and magnetic orders which can be expected to lie at the heart of new Skyrmion control paradigms. The use of ME coupling for Skyrmion manipulation is also attractive for applications since losses due to Joule heating are negligible. Presently, however, open questions remain concerning the basic understanding of how an applied E field can manipulate the Skyrmion spin texture. To address this issue, we have used small-angle neutron scattering (SANS) to study the giant E-field-induced SKL rotations generated in a bulk sample of ME Cu 2 OSeO 3 . Surprisingly, the rotations saturate at an angle dependent on both the size and sign of the E field. With supporting calculations, we explain our observations, and show that an E-field-induced Skyrmion distortion leads to the observed rotations. This amounts to a new approach for Skyrmion control that does not require STTs.In Cu 2 OSeO 3 , the ME coupling exists in all magnetic phases [12,[21][22][23][24][25][26][27][28], and is generated by the d-p hybridization mechanism [12,24,29,30]. This mechanism dictates a particular ME coupling anisotropy; for a magnetic field μ 0 H∥½110 or [111], an electric polarization P emerges ∥½001 or [111], respectively [24]. In our experiments, we chose E∥½111 (which corresponds to a negative applied voltage) or ∥½111 (positive voltage). T...
Small-angle neutron scattering has been employed to study the influence of applied electric (E-)fields on the skyrmion lattice in the chiral lattice magnetoelectric Cu(2)OSeO(3). Using an experimental geometry with the E-field parallel to the [111] axis, and the magnetic field parallel to the [11(-)0] axis, we demonstrate that the effect of applying an E-field is to controllably rotate the skyrmion lattice around the magnetic field axis. Our results are an important first demonstration for a microscopic coupling between applied E-fields and the skyrmions in an insulator, and show that the general emergent properties of skyrmions may be tailored according to the properties of the host system.
Out of the 14 lanthanide (Ln) ions, molecular complexes of Ln(IV) were known only for cerium and more recently terbium. Here we demonstrate that the +IV oxidation state is also accessible for the large praseodymium (Pr) cation. The oxidation of the tetrakis(triphenysiloxide) Pr(III) ate complex, [KPr(OSiPh 3 ) 4 (THF) 3 ], 1-Pr Ph , with [N(C 6 H 4 Br) 3 ][SbCl 6 ], affords the Pr(IV) complex [Pr(OSiPh 3 ) 4 (MeCN) 2 ], 2-Pr Ph , which is stable once isolated. The solid state structure, UV−visible spectroscopy, magnetometry, and cyclic voltammetry data along with the DFT computations of the 2-Pr Ph complex unambiguously confirm the presence of Pr(IV).
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