The initial employment of the fluorescent bridging ligand naphthalene-2,3-diol in 4f-metal coordination chemistry has provided access to a new family of Ln(III)8 clusters with a "Christmas-star" topology, single-molecule magnetism behavior, and ligand-centered emissions.
The employment of di-2-pyridyl ketone, (py)CO, in heterometallic Mn/4f and homometallic Mn cluster chemistry has yielded six MnLn and two MnMn structurally related clusters, namely, [MnLnO{(py)CO}(NO)(RCO)(HO)](NO) (Ln = Gd, 1, 5; Dy, 2; Tb, 3; R = Et, 1-3; Me, 5), [MnDyO{(py)CO}(NO)(EtCO)(HO)(MeOH)]·0.7MeOH·0.8HO (4·0.7MeOH·0.8HO), [MnGdO{(py)CO}(NO)(CHClCO)(MeOH)(py)]·2MeOH (6·2MeOH), [MnO{(py)CO}(py)(HO)](ClO)·4HO (7·4HO), and [MnO{(py)CO}(NO)(py)] (8), where (py)CO is the dianion of the gem-diol derivative of (py)CO. The compounds possess a new type of cross-shaped structural core, which in the case of 1-6 is essentially planar, whereas in 7 and 8 it deviates from planarity. Clusters 1-6 are rare examples of Mn/4f species bearing (py)CO or its derivatives, despite the fact that this ligand has been well-studied and proven a rich source of more than 200 metal compounds so far. Variable-temperature, solid-state direct-current and alternating-current magnetization studies were performed on complexes 1-5, 7, and 8 revealing that the dominant exchange interactions between the metal ions are antiferromagnetic and indicating ground-state spin values of S = 5 (for 1), 6 (for 5), and 2 (for 7 and 8).
A new member of the Mn family of single-molecule magnets (SMMs) has been prepared and found to be the first of this family to give a 3-D ferromagnetic network. [MnO(OCCH-p-F)(HO)] (2) was prepared by carboxylate substitution on the acetate derivative with p-F-benzoic acid and crystallizes as 2·8MeCN in space group I4̅2m with extensive formation of intermolecular C-H···F hydrogen-bonding. The latter leads to a combination of ferromagnetic (F) and antiferromagnetic (AF) interactions and an overall F network that gives a χT value at low T that is abnormally high for an S = 10 ground state. 2·8MeCN undergoes solvent loss under vacuum to 2, with a decrease in unit-cell volume of 17%, primarily due to a 13% decrease in the c-axis. The χT vs T plot for 2 indicates a switch to a net AF network. Exposure to air causes hydration to 2·3HO, a concomitant increase in unit cell volume, and a switch back to a F network. The same conversion of 2·8MeCN to 2·3HO can also be accomplished in one step rather than two steps, by leaving crystals of the former exposed to air at ambient temperature and pressure for 10 days, giving the same magnetic plots. Interestingly, the desolvation/solvation processes cause Jahn-Teller isomerism to occur, but the ratio of the faster-relaxing isomer to the normal slowly relaxing one does not change monotonically. Single-crystal micro-SQUID studies on 2·8MeCN show the expected magnetization hysteresis loops for a SMM and a small exchange-bias from the intermolecular interactions that is unexpectedly AF. Since the micro-SQUID study only identifies interactions along the easy-axis (z-axis) of the crystal, this is readily rationalized as due to the J components of the intermolecular interactions in 2·8MeCN being net AF. The combined results offer useful insights into the degree of sensitivity of the magnetic properties to small environmental perturbations.
Three new nanosized clusters and single molecule magnets ([Mn24] and [Mn23]) with uncommon supertetrahedral T4 – like Mn/O cores prepared from the combination of pdH2 with (py)2CO in Mn cluster chemistry are reported.
The symmetry of single-molecule magnets dictates their spin quantum dynamics, influencing how such systems relax via quantum tunneling of magnetization (QTM). By reducing a system's symmetry, through the application of a magnetic field or uniaxial pressure, these dynamics can be modified. We report measurements of the magnetization dynamics of a crystalline sample of the high-symmetry [Mn12O12(O2CMe)16(MeOH)4] · MeOH single-molecule magnet as a function of uniaxial pressure applied either parallel or perpendicular to the sample's "easy" magnetization axis.At temperatures between 1.8 and 3.3 K, magnetic hysteresis loops exhibit the characteristic steplike features that signal the occurrence of QTM. After applying uniaxial pressure to the sample in situ, both the magnitude and field position of the QTM steps changed. The step magnitudes were observed to grow as a function of pressure in both arrangements of pressure, while pressure applied along (perpendicular to) the sample's easy axis caused the resonant-tunneling fields to increase (decrease). These observations were compared with simulations in which the system's Hamiltonian parameters were changed. From these comparisons, we determined that parallel pressure induces changes to the second-order axial anisotropy parameter as well as either the fourth-order axial or fourth-order transverse parameter, or to both. In addition, we find that pressure applied
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