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Abstract:

We examine the crystal structures and magnetic properties of several S = 1 Ni(II) coordination compounds, molecules and polymers, that include the bridging ligands HF2−, AF62− (A = Ti, Zr) and pyrazine or non-bridging ligands F−, SiF62−, glycine, H2O, 1-vinylimidazole, 4-methylpyrazole and 3-hydroxypyridine. Pseudo-octahedral NiN4F2, NiN4O2 or NiN4OF cores consist of equatorial Ni-N bonds that are equal to or slightly longer than the axial Ni-Lax bonds. By design, the zero-field splitting (D) is large in these systems and, in the presence of substantial exchange interactions (J), can be difficult to discriminate from magnetometry measurements on powder samples. Thus, we relied on pulsed-field magnetization in those cases and employed electron-spin resonance (ESR) to confirm D when J ≪ D. The anisotropy of each compound was found to be easy-plane (D > 0) and range from ≈ 8–25 K. This work reveals a linear correlation between the ratio d(Ni-Lax)/d(Ni-Neq) and D although the ligand spectrochemical properties may play an important role. We assert that this relationship allows us to predict the type of magnetocrystalline anisotropy in tailored Ni(II) quantum magnets.

Abstract:

We present the results of muon-spin relaxation ([Formula: see text]SR) measurements on antiferromagnetic and ferromagnetic spin chains. In antiferromagnetic CuF2(pyz) we identify a transition to long range magnetic order taking place at [Formula: see text] K, allowing us to estimate a ratio with the intrachain exchange of [Formula: see text] and the ratio of interchain to intrachain exchange coupling as [Formula: see text]. The ferromagnetic chain [Sm(hfac)3(boaDTDA)] n undergoes an ordering transition at [Formula: see text] K, seen via a broad freezing of dynamic fluctuations on the muon (microsecond) timescale and implying [Formula: see text]. The ordered radical moment continues to fluctuate on this timescale down to 0.3 K, while the Sm moments remain disordered. In contrast, the radical spins in [La(hfac)3(boaDTDA)] n remain magnetically disordered down to T  =  0.1 K suggesting [Formula: see text].