Regulating the magnetic properties of seven-coordinated Dy(III) single-ion magnets through the effect of positional isomers on axial crystal-field.

Six Dy(III) single-ion magnets (SIMs) [Dy(n-OMe-bbpen)X] were synthesized by a solvothermal reaction with three positional isomers (ortho, meta, and para) of ligands n-OMe-H2bbpen and dysprosium halides DyX3, (n-OMe-H2bbpen = N,N'-bis(2-hydroxy-n-methoxybenzyl)-N,N'-bis(2-methylpyridyl)ethylenediamine; n = 3, X = Cl, 1; n = 3, X = Br, 2; n = 4, X = Cl, 3; n = 4, X = Br, 4; n = 5, X = Cl, 5; n = 5, X = Br, 6). Dynamic magnetic measurements revealed that the six complexes possess notably different effective barriers of magnetic reversal: 872.0 K (1), 1210.1 K (2), 137.9 K (3), 602.6 K (4), 907.0 K (5) and 1216.7 K (6). 6 showed the best performance as SIMs among the six Dy(III) complexes. Moreover, the magnetic hysteresis loops of 6 remained open at 21 K. The crystal structures indicate the switching of local symmetry around Dy(III) ion, aroused by the variation in intermolecular interactions and steric effects. This switch is primarily correlated with the distinction of magnetic properties. In addition, ab initio calculations confirmed that the different electrostatic potential around Dy(III) ion stemming from the electronic effect of the OMe-substituted group is another factor leading to the distinction in magnetic properties. This work warns us that when designing ligands for Dy-SIMs, the effect of positional isomerism on magnetic performance must be considered, which is one of the factors that can easily be overlooked.

Improving the single-molecule magnet properties of two pentagonal bipyramidal Dy3+ compounds by the introduction of both electron-withdrawing and -donating groups.

Two mononuclear Dy3+ compounds [Dy(bmbpen-F)X] (X = Cl, 1; Br, 2) with a pentagonal bipyramidal (PBP) geometry were obtained from N,N'-bis-(5-methyl-2-hydroxybenzyl)-N,N'-bis(5-fluoro-2-methylpyridyl)ethylenediamine (H2bmbpen-F) and dysprosium halides. The magnetic anisotropy and single-molecule magnet (SMM) behavior of these PBP compounds were regulated by introducing both electron-withdrawing F atoms into the equatorial pyridine rings and electron-donating -CH3 groups into the axial phenolic hydroxyl rings. The results of magnetic characterization show that 1 and 2 exhibit single molecule magnet behavior with magnetization reversal barriers of 990(13) and 1189(16) K under a zero dc external field and magnetic hysteresis loops up to 26 K and 36 K, respectively. The results of ab initio calculations are consistent with the experimental observations, confirming that the simultaneous introduction of electron-withdrawing groups into the equatorial positions and electron-donating groups into the axial positions can lead to PBP Dy-SMMs with improved properties.

Symmetry Breaking and Two-Step Spin-Crossover Behavior in Two Cyano-Bridged Mixed-Valence {FeIII2(µ-CN)4FeII2} Clusters.

Two new cyano-bridged mixed-valence {FeIII2(µ-CN)4FeII2} clusters, {[(Tp)FeIII(CN)3]2[FeII(Py2N2)]2}·(ClO4)2·MeCN·Et2O (1·MeCN·Et2O), its solvent-free form (1), and {[(Tp)FeIII(CN)3]2[FeII(Me2Py2N2)]2}·(ClO4)2·5MeOH (2·5MeOH), were obtained [Tp = hydrotris(pyrazol-1-yl)borate; N,N'-bis(2-pyridylmethyl)-N,N'-bis(4-X-benzyl)-1,2-ethanediamine, Py2N2, X = H; Me2Py2N2, X = Me]. Complexes 1 and 2·5MeOH exhibit gradual thermally induced two-step spin-crossover behavior (SCO) at two FeII metal centers, and the transformation of high-spin (HS) to low-spin (LS) FeII ions with temperature was confirmed by a combination of X-ray crystallography, variable-temperature Fourier transform infrared, variable-temperature magnetic susceptibility, and 57Fe Mössbauer spectroscopy. Moreover, complexes 1·MeCN·Et2O and 1 exhibit a reversible single-crystal-to-single-crystal transformation, and complex 1 undergoes two-step SCO behavior with T1/2 = 178 and 93 K accompanied by symmetry breaking in the structure.

Multistep Oxidation of Diethynyl Oligophenylamine-Bridged Diruthenium and Diiron Complexes.

Homo-dinuclear nonlinear complexes [{M(dppe)Cp*}2{µ-(-C≡C)2X}] (dppe = 1,2-bis(diphenylphosphino)ethane; Cp* = η5-C5Me5; X = triphenylamine (TPA), M = Ru (1a) and Fe (1b); X = N,N,N',N'-tetraphenylphenylene-1,4-diamine (TPPD), M = Ru (2a)) were prepared and characterized by 1H, 13C, and 31P NMR spectroscopy and single-crystal X-ray diffraction (1a, 2a). Attempts to prepare the diiron analogue of 2a were not successful. Experimental data obtained from cyclic voltammetry, square wave voltammetry, UV-vis-NIR (NIR = near-infrared) spectro-electrochemistry, and very informative IR spectro-electrochemistry in the C≡C stretching region, combined with density functional theory calculations, afford to make an emphasizing assessment of the close association between the metal-ethynyl termini and the oligophenylamine bridge core as well as their respective involvement in sequential one-electron oxidations of these complexes. The anodic behavior of the homo-bimetallic complexes depends strongly both on the metal center and the length of the oligophenylamine bridge core. The poorly separated first two oxidations of diiron complex 1b are localized on the electronically nearly independent Fe termini. In contrast, diruthenium complex 1a exhibits a significantly delocalized character and a marked electronic communication between the ruthenium centers through the diethynyl-TPA bridge. The ruthenium-ethynyl halves in 2a, separated by the doubly extended and more flexible TPPD bridge core, show a lower degree of electronic coupling, resulting in close-lying first two anodic waves and the NIR electronic absorption of [2a]+ with an indistinctive intervalence charge transfer character. Finally, the third anodic waves in the voltammetric responses of the homo-bimetallic complexes are associated with the concurrent exclusive oxidation of the TPA or TPPD bridge cores.