Stress‐induced Domain Wall Motion in a Ferroelastic Mn3+ Spin Crossover Complex

Domain wall motion is detected for the first time during the transition to a ferroelastic and spin‐state ordered phase of a spin crossover complex. Single crystal X‐ray diffraction and resonant ultrasonic spectroscopy (RUS) revealed two distinct symmetry‐breaking phase transitions in the mononuclear Mn 3+ compound [Mn(3,5‐diBr‐sal 2 (323))]BPh 4 , 1. The first at 250 K, involves the space group change Cc → Pc and is thermodynamically continuous, while the second, Pc → P1 at 85 K, is discontinuous and related to spin crossover and spin‐state ordering. Stress‐induced domain wall mobility was detected as softening of the phonon modes at the Pc → P1 transition

Giant Magnetoelectric Coupling and Magnetic-Field-Induced Permanent Switching in a Spin Crossover Mn(III) Complex

International audienceWe investigate giant magnetoelectric coupling at a Mn spin crossover in [MnL]BPh (L = (3,5-diBr-sal)323) with a field-induced permanent switching of the structural, electric, and magnetic properties. An applied magnetic field induces a first-order phase transition from a high spin/low spin (HS-LS) ordered phase to a HS-only phase at 87.5 K that remains after the field is removed. We observe this unusual effect for DC magnetic fields as low as 8.7 T. The spin-state switching driven by the magnetic field in the bistable molecular material is accompanied by a change in electric polarization amplitude and direction due to a symmetry-breaking phase transition between polar space groups. The magnetoelectric coupling occurs due to a γη coupling between the order parameter γ related to the spin-state bistability and the symmetry-breaking order parameter η responsible for the change of symmetry between polar structural phases. We also observe conductivity occurring during the spin crossover and evaluate the possibility that it results from conducting phase boundaries. We perform ab initio calculations to understand the origin of the electric polarization change as well as the conductivity during the spin crossover. Thus, we demonstrate a giant magnetoelectric effect with a field-induced electric polarization change that is 1/10 of the record for any material

Assignment of solid-state ¹³C and ¹H NMR spectra of paramagnetic Ni(II) acetylacetonate complexes aided by first-principles computations

Abstract Recent advances in computational methodology allowed for first-principles calculations of the nuclear shielding tensor for a series of paramagnetic nickel(II) acetylacetonate complexes, [Ni(acac)₂L₂] with L = H₂O, D₂O, NH₃, ND₃, and PMe₂Ph have provided detailed insight into the origin of the paramagnetic contributions to the total shift tensor. This was employed for the assignment of the solid-state ¹,²H and ¹³C MAS NMR spectra of these compounds. The two major contributions to the isotropic shifts are by orbital (diamagnetic-like) and contact mechanism. The orbital shielding, contact, as well as dipolar terms all contribute to the anisotropic component. The calculations suggest reassignment of the ¹³C methyl and carbonyl resonances in the acac ligand [Inorg. Chem. 53, 2014, 399] leading to isotropic paramagnetic shifts of δ(¹³C) ≈ 800–1100 ppm and ≈180–300 ppm for ¹³C for the methyl and carbonyl carbons located three and two bonds away from the paramagnetic Ni(II) ion, respectively. Assignment using three different empirical correlations, i.e., paramagnetic shifts, shift anisotropy, and relaxation (T₁) were ambiguous, however the latter two support the computational results. Thus, solid-state NMR spectroscopy in combination with modern quantum-chemical calculations of paramagnetic shifts constitutes a promising tool for structural investigations of metal complexes and materials