No abstract

Two mononuclear seven-coordinate cobalt(II) complexes [Co(L)3(NO3)2] (L = 4-tert-butylpyridine, 1; L = isoquinoline, 2) were prepared and structurally analyzed by single-crystal X-ray crystallography. The coordination spheres of 1 and 2 exhibit distorted pentagonal bipyramid geometry. Analysis of their direct-current magnetic data reveals the existence of easy plane anisotropy (D > 0) with a small transverse anisotropy (E), which was further confirmed by high-field electron paramagnetic resonance (HFEPR) spectroscopy. Field-induced slow magnetic relaxations were observed under the applied dc field in complexes 1 and 2 by alternating-current magnetic susceptibility measurements. Importantly, these complexes are new instances of mononuclear high-coordinate cobalt(II)-based single-molecule magnets.

Ionic hydrogenation has not been extensively explored, but is advantageous for challenging substrates such as unsaturated intermediates. Reported here is an iridium‐catalyzed hydrogenation of oxocarbenium ions to afford chiral isochromans with high enantioselectivities. A variety of functionalities are compatible with this catalytic system. In the presence of a catalytic amount of the Brønsted acid HCl, an α‐chloroether is generated in situ and subsequentially reduced. Kinetic studies suggest first‐order kinetics in the substrate and half‐order kinetics in the catalyst. A positive nonlinear effect, together with the half kinetic order, revealed a dimerization of the catalyst. Possible reaction pathways based on the monomeric iridium catalyst were proposed and DFT computational studies revealed an ionic hydrogenation pathway. Chloride abstraction and the cleavage of dihydrogen occur in the same step.

The magnetic structures of the intrinsic magnetic topological insulator family MnBi2Te4(Bi2Te3)n (n = 0, 1, 2) adopt A-type antiferromagnetic (AFM) configurations with ferromagnetic (FM) MnBi2Te4 layers stacking through van der Waals interactions. While the interlayer coupling could be effectively tunned by the number of Bi2Te3 spacer layers n, the intralayer FM exchange coupling is considered too robust to control. Here, by applying hydrostatic pressure up to 3.5 GPa as an external knob, we discover the opposite responses of magnetic properties for MnBi2Te4(Bi2Te3)n with n = 1 and 2. In MnBi4Te7, the Né el temperature decreases with an increasing saturation field as pressure increases, indicating an enhanced interlayer AFM coupling. In sharp contrast, both the magnetic susceptibility and magneto-tranport measurements show that MnBi6Te10 experiences a phase transition from A-type AFM to quasi two-dimensional FM state with a suppressed saturation field under pressure. First-principles calculations reveal the essential role of the intralayer exchange coupling, which contains the competition between the AFM-preferred direct exchange and FM-preferred superexchange coupling, in determining these magnetic properties. Such a magnetic phase transition is also observed in Sb-doped MnBi6Te10 due to similar mechanism, where the in-plane lattice constant is effectively reduced.

Three mononuclear cobalt(II) tetranitrate complexes (A)[Co(NO)] with different countercations, PhP (1), MePhP (2), and PhAs (3), have been synthesized and studied by X-ray single-crystal diffraction, magnetic measurements, inelastic neutron scattering (INS), high-frequency and high-field EPR (HF-EPR) spectroscopy, and theoretical calculations. The X-ray diffraction studies reveal that the structure of the tetranitrate cobalt anion varies with the countercation. 1 and 2 exhibit highly irregular seven-coordinate geometries, while the central Co(II) ion of 3 is in a distorted-dodecahedral configuration. The sole magnetic transition observed in the INS spectroscopy of 1-3 corresponds to the zero-field splitting (2(D + 3E)) from 22.5(2) cm in 1 to 26.6(3) cm in 2 and 11.1(5) cm in 3. The positive sign of the D value, and hence the easy-plane magnetic anisotropy, was demonstrated for 1 by INS studies under magnetic fields and HF-EPR spectroscopy. The combined analyses of INS and HF-EPR data yield the D values as +10.90(3), +12.74(3), and +4.50(3) cm for 1-3, respectively. Frequency- and temperature-dependent alternating-current magnetic susceptibility measurements reveal the slow magnetization relaxation in 1 and 2 at an applied dc field of 600 Oe, which is a characteristic of field-induced single-molecule magnets (SMMs). The electronic structures and the origin of magnetic anisotropy of 1-3 were revealed by calculations at the CASPT2/NEVPT2 level.

No abstract

No abstract

No abstract