Terminal and Internal Alkyne Complexes and Azide-Alkyne Cycloaddition Chemistry of Copper(I) Supported by a Fluorinated Bis(pyrazolyl)borate

Copper plays an important role in alkyne coordination chemistry and transformations. This report describes the isolation and full characterization of a thermally stable, copper(I) acetylene complex using a highly fluorinated bis(pyrazolyl)borate ligand support. Details of the related copper(I) complex of HCºCSiMe3 are also reported. They are three-coordinate copper complexes featuring η2-bound alkynes. Raman data show significant red-shifts in CºC stretch of [H2B(3,5-(CF3)2Pz)2]Cu(HCºCH) and [H2B(3,5-(CF3)2Pz)2]Cu(HCºCSiMe3) relative to those of the corresponding alkynes. Computational analysis using DFT indicates that the Cu(I) alkyne interaction in these molecules is primarily of the electrostatic character. The π-backbonding is the larger component of the orbital contribution to the interaction. The dinuclear complexes such as Cu2(μ-[3,5-(CF3)2Pz])2(HCºCH)2 display similar Cu-alkyne bonding features. The mononuclear [H2B(3,5-(CF3)2Pz)2]Cu(NCMe) complex catalyzes [3+2] cycloadditions between tolyl azide and a variety of alkynes including acetylene. It is comparatively less effective than the related trinuclear copper catalyst {μ-[3,5-(CF3)2Pz]Cu}3 involving bridging pyrazolates.

Study of Integer Spin S = 1 in the Polar Magnet β-Ni(IO3)2

Polar magnetic materials exhibiting appreciable asymmetric exchange interactions can potentially host new topological states of matter such as vortex-like spin textures; however, realizations have been mostly limited to half-integer spins due to rare numbers of integer spin systems with broken spatial inversion lattice symmetries. Here, we studied the structure and magnetic properties of the S = 1 integer spin polar magnet β-Ni(IO3)2 (Ni2+, d8, 3F). We synthesized single crystals and bulk polycrystalline samples of β-Ni(IO3)2 by combining low-temperature chemistry techniques and thermal analysis and characterized its crystal structure and physical properties. Single crystal X-ray and powder X-ray diffraction measurements demonstrated that β-Ni(IO3)2 crystallizes in the noncentrosymmetric polar monoclinic structure with space group P21. The combination of the macroscopic electric polarization driven by the coalignment of the (IO3)− trigonal pyramids along the b axis and the S = 1 state of the Ni2+ cation was chosen to investigate integer spin and lattice dynamics in magnetism. The effective magnetic moment of Ni2+ was extracted from magnetization measurements to be 3.2(1) µB, confirming the S = 1 integer spin state of Ni2+ with some orbital contribution. β-Ni(IO3)2 undergoes a magnetic ordering at T = 3 K at a low magnetic field, μ0H = 0.1 T; the phase transition, nevertheless, is suppressed at a higher field, μ0H = 3 T. An anomaly resembling a phase transition is observed at T ≈ 2.7 K in the Cp/T vs. T plot, which is the approximate temperature of the magnetic phase transition of the material, indicating that the transition is magnetically driven. This work offers a useful route for exploring integer spin noncentrosymmetric materials, broadening the phase space of polar magnet candidates, which can harbor new topological spin physics.

Twisted magnetization phases in orbital-dominant rare-earth nitrides

<p>In this thesis we investigate the magnetic properties of NdN and SmN, members of the rare-earth nitrides, a series of intrinsic ferromagnetic semiconductors. In rare-earth systems, the strong spin-orbit coupling of the partially filled 4ƒ shell ensures that there is a substantial orbital contribution to the ferromagnetic moment, in contrast to many transition metal systems where the orbital moment is usually quenched. In SmN and NdN the orbital moment actually exceeds the spin moment, and the resulting orbital dominant magnetization allows for the fabrication of a magnetic heterostructures showing novel behavior. We report a new theoretical study of the magnetic properties on both SmN and NdN by considering the atomic-like 4ƒ electrons. These calculations incorporate spin-orbit coupling, the exchange interaction in a self-consistent mean-field approach, and crystal field interactions in an arbitrary-multiplet point-charge model. Our findings show excellent agreement with the experimentally measured ferromagnetic moments of SmN and NdN, representing an advance from previous theoretical studies. We also report an experimental study on SmN/GdN heterostructures using the element-resolved method of x-ray magnetic circular dichroism (XMCD) to probe the magnetism. The competition between the orbital-dominant Zeeman coupling in SmN and the ferromagnetic spin-based interface exchange with GdN, which has purely a spin moment, results in a twisted magnetization profile. The depth profile of the magnetization derived from XMCD measurements showed good agreement with an analytical model developed to describe the competing interactions. In a second study, a superlattice of NdN/GdN was investigated via XMCD and standard magnetometry techniques. A twisted magnetization was shown to be present due to the same mechanism as in the SmN/GdN system. By varying the maximum applied field and temperature, twisted phases were shown to develop in both GdN and NdN layers. These twisted phases in orbital-dominant ferromagnetic semiconductors represent a departure from previously explored spin-dominant metallic systems displaying similar twisted phases.</p>

Twisted magnetization phases in orbital-dominant rare-earth nitrides

<p>In this thesis we investigate the magnetic properties of NdN and SmN, members of the rare-earth nitrides, a series of intrinsic ferromagnetic semiconductors. In rare-earth systems, the strong spin-orbit coupling of the partially filled 4ƒ shell ensures that there is a substantial orbital contribution to the ferromagnetic moment, in contrast to many transition metal systems where the orbital moment is usually quenched. In SmN and NdN the orbital moment actually exceeds the spin moment, and the resulting orbital dominant magnetization allows for the fabrication of a magnetic heterostructures showing novel behavior. We report a new theoretical study of the magnetic properties on both SmN and NdN by considering the atomic-like 4ƒ electrons. These calculations incorporate spin-orbit coupling, the exchange interaction in a self-consistent mean-field approach, and crystal field interactions in an arbitrary-multiplet point-charge model. Our findings show excellent agreement with the experimentally measured ferromagnetic moments of SmN and NdN, representing an advance from previous theoretical studies. We also report an experimental study on SmN/GdN heterostructures using the element-resolved method of x-ray magnetic circular dichroism (XMCD) to probe the magnetism. The competition between the orbital-dominant Zeeman coupling in SmN and the ferromagnetic spin-based interface exchange with GdN, which has purely a spin moment, results in a twisted magnetization profile. The depth profile of the magnetization derived from XMCD measurements showed good agreement with an analytical model developed to describe the competing interactions. In a second study, a superlattice of NdN/GdN was investigated via XMCD and standard magnetometry techniques. A twisted magnetization was shown to be present due to the same mechanism as in the SmN/GdN system. By varying the maximum applied field and temperature, twisted phases were shown to develop in both GdN and NdN layers. These twisted phases in orbital-dominant ferromagnetic semiconductors represent a departure from previously explored spin-dominant metallic systems displaying similar twisted phases.</p>

Assessing the Orbital Contribution in the “Spodium Bond” by Natural Orbital for Chemical Valence-Charge Displacement Analysis

<p>The term “spodium bond” (SpB) has been recently proposed for the non-coordinative interaction between a polarised group 12 metal and a mild Lewis base. In most of the systems showing short metal-donor distances, however, SpB coexists with other weak interactions, including hydrogen and halogen bonding. Here we show their mutual importance can be probed by dissecting the orbital component of the interaction through the Natural Orbital for Chemical Valence-Charge Displacement analysis. NOCV-CD gives us straightforward snapshots of relative energies and electrons involved, either for model and “real” adducts, allowing us to demonstrate the lack of a direct correlation between a favourable metal-base distance and the presence of an orbital contribution for the SpB.</p>

Фазовые переходы и фазовые превращения в нанообластях фазового расслоения в мультиферроике ErMn-=SUB=-2-=/SUB=-O-=SUB=-5-=/SUB=-

The effect of the rare-earth ion Er3+, which has a large orbital contribution to the magnetic moment, were studied to phase transitions and phase transformations of 2D nanoregions of phase separation in the ErMn2O5 multiferroic. These nanoregions are the semiconductor heterostructures (superlattices) and are formed due to self-organization processes in the ErMn2O5 matrix. Significant effect of Er3+ ions, the moments of which are rigidly oriented along the c axis of the crystal, on the magnetic dynamics, heat capacity and multiferroic properties of layers superlattises was found at a wide temperature range 5 K - 300 K in ErMn2O5 multiferroics.

Assessing the Orbital Contribution in the “Spodium Bond” by Natural Orbital for Chemical Valence-Charge Displacement Analysis

<p>The term “spodium bond” (SpB) has been recently proposed for the non-coordinative interaction between a polarised group 12 metal and a mild Lewis base. In most of the systems showing short metal-donor distances, however, SpB coexists with other weak interactions, including hydrogen and halogen bonding. Here we show their mutual importance can be probed by dissecting the orbital component of the interaction through the Natural Orbital for Chemical Valence-Charge Displacement analysis. NOCV-CD gives us straightforward snapshots of relative energies and electrons involved, either for model and “real” adducts, allowing us to demonstrate the lack of a direct correlation between a favourable metal-base distance and the presence of an orbital contribution for the SpB.</p>