The preparation, characterization, and X-ray structure are reported for the single-molecule magnet (PPh4)[Mn12O12(O2CPh)16(H2O)4]·8(CH2Cl2) (2). Complex 2 crystallizes in the triclinic space group P1̄, which at 213 K has a = 17.2329(2), b = 17.8347(2), c = 26.8052(2) Å, α = 90.515(2), β = 94.242(2), γ = 101.437(2)°, and Z = 2. The salt consists of PPh4 + cations and [Mn12O12(O2CPh)16(H2O)4]- anions. The (Mn12O12)15+ core of the anion is formed by an external ring of eight Mn atoms bridged by μ3−O2- ions to an internal tetrahedron of four Mn atoms. Because of disorder in both phenyl rings and solvate molecules, it was difficult to use bond valence sum values to determine definitively the oxidation state of each Mn atom. There is a Mn4O4 cubane unit in the internal part of the molecule and these Mn atoms are all MnIV ions. For the eight “external” Mn atoms the bond valence sum values did not define well their oxidation states. For these eight Mn atoms, it was not possible to determine whether a trapped-valence MnIIMnIII 7 or an electronically delocalized description is appropriate. High-frequency EPR (HFEPR) data were collected for the previously structurally characterized MnIV 4MnIII 7MnII valence-trapped salt (PPh4)[Mn12O12(O2CEt)16(H2O)4] (1) at 328.2 and 437.69 GHz. In the high magnetic field the crystallites orient and the HFEPR spectra are pseudo−single-crystal like, not powder patterns. The spectral features are attributed to the fine structure expected for a S = 19/2 complex experiencing axial zero-field splitting D Ŝ z 2, where D = −0.62 cm-1. The sign of D was definitively determined by the temperature dependence of the spectrum. Complex 2 exhibits one out-of-phase ac magnetic susceptibility (χ‘ ‘M) signal in the 3−6 K range. The temperature of the χ‘ ‘M peak is frequency dependent, as expected for a single-molecule magnet. The rate at which the direction of magnetization reverses from “up” to “down” was evaluated from χ‘ ‘M data collected at various frequencies (1−1512 Hz) of oscillation of the ac magnetic field. This gives magnetization relaxation rates in the 2.86−4.51 K range for complex 2 and in the 3.2−7.2 K range for complex 1. Rates were also determined in the 1.80−2.50 K range for complex 1 via magnetization decay experiments. In this latter case, the polycrystalline sample is magnetically saturated in a large dc field. After the magnetic field is rapidly decreased to zero, the decay of the magnetization to zero is monitored. The rates evaluated by both the frequency dependence of the out-of-phase ac signal and dc relaxation decay experiments for complex 1 fit on an Arrhenius plot to give an activation energy of U eff = 57 K and a preexponential rate of 1/τ0 = 7.2 × 107 s-1. From the HFEPR data, complex 1 has a S = 19/2 ground state with D = −0.62 cm-1. This gives a potential-energy barrier of U = 79 K for the double-well potential-energy diagram. The value of U eff is less than the barrier height U, because when individual [Mn12 -] anions convert from spin “up” to spin “down”, they can not only...

Reactions of VCl3(THF)3, bpy, and NaO2CR (R = Et, Ph; bpy = 2,2‘-bipyridine) in a 1:1:3 ratio in Me2CO give [V4O2(O2CR)7(bpy)2](ClO4) (R = Et, 1; R = Ph, 4) following addition of NBun 4ClO4. Use of 4,4‘-dimethyl- or 5,5‘-dimethylbipyridine (4,4‘-Me2bpy and 5,5‘-Me2bpy, respectively) and R = Et leads similarly to [V4O2(O2CEt)7(L−L)2](ClO4) (L−L = 4,4‘-Me2bpy, 2; L−L = 5,5‘-Me2bpy, 3). Yields are in the 38−90% range. The cation of 1 is isostructural with previously prepared [M4O2(O2CR)7(bpy)2]+ (M = CrIII, MnIII, FeIII) species and possesses a [V4O2] butterfly core. 1D and 2D COSY 1H NMR spectra of 1 show the solid-state structure is retained on dissolution. The effective magnetic moment (μeff) per V4 for 1 gradually rises from 5.79 μB at 300 K to a maximum of 6.80 μB at 25.0 K and then decreases rapidly to 4.72 μB at 2.00 K. The data in the 7.00−300 K range were fit to the appropriate theoretical expression (based on Ĥ = −2JS i ·S j ) to give J bb = −31.2 cm-1, J wb = +27.5 cm-1, and g = 1.82, (b = body, w = wingtip). These values indicate a S T = 3 ground state, confirmed by magnetization vs field studies. Similar results were obtained for the 2-picolinate (pic) analogue of 1 (complex 5). The S T = 3, 1, 3, and 0 ground states for the M = VIII, CrIII, MnIII, and FeIII, respectively, are rationalized using spin frustration arguments based on competition between J bb and J wb interactions. AC magnetic susceptibility studies down to 1.7 K on 1 and 5 show weak out-of-phase signals (χ‘‘M) below 4.0 K and corresponding small decreases in the in-phase signals (χ‘M), indicating that the relaxation of magnetization is unusually slow and comparable with the oscillating AC field (250−1000 Hz). This is a characteristic signature of a single-molecule magnet. Simultaneous application of AC and DC fields has the effect of increasing the barrier to magnetization relaxation, causing the χ‘‘M signal to move to higher temperature and consequently leading to a much stronger χ‘‘M signal and, for 5, the observation of a peak at ∼2.0 K. A dependence of the χ‘‘M peak position of 5 on the DC field intensity and AC field oscillation frequency is found.

Several single-molecule magnets with the composition [Mn12O12(O2CR)16(H2O)x] (x = 3 or 4) exhibit two out-of-phase ac magnetic susceptibility signals, one in the 4-7 K region and the other in the 2-3 K region. New Mn12 complexes were prepared and structurally characterized, and the origin of the two magnetization relaxation processes was systematically examined. Different crystallographic forms of a Mn12 complex with a given R substituent exist where the two forms have different compositions of solvent molecules of crystallization and this results in two different arrangements of bound H2O and carboxylate ligands for the two crystallographically different forms with the same R substituent. The X-ray structure of cubic crystals of [Mn12O12(O2CEt)16(H2O)3]. 4H2O (space group P1) (complex 2a) has been reported previously. The more prevalent needle-form of [Mn12O12(O2CEt)16(H2O)3] (complex 2b) crystallizes in the monoclinic space group P2(1)/c, which at -170 degrees C has a = 16.462(7) A, b = 22.401(9) A, c = 20.766(9) A, beta = 103.85(2) degrees, and Z = 4. The arrangements of H2O and carboxylate ligands on the Mn12 molecule are different in the two crystal forms. The complex [Mn12O12-(O2)CC6H4-p-Cl)16(H2O)4].8CH2Cl2 (5) crystallizes in the monoclinic space group C2/c, which at -172 degrees C has a = 29.697(9) A, b = 17.708(4) A, c = 30.204(8) A, beta = 102.12(2) degrees, and Z = 4. The ac susceptibility data for complex 5 show that it has out-of-phase signals in both the 2-3 K and the 4-7 K ranges. X-ray structures are also reported for two isomeric forms of the p-methylbenzoate complex. [Mn12O12(O2CC6H4-p-Me)16(H2O)4]. (HO2CC6H4-p-Me) (6) crystallizes in the monoclinic space group C2/c, which at 193 K has a = 40.4589(5) A, b = 18.2288(2) A, c = 26.5882(4) A, beta = 125.8359(2) degrees, and Z = 4. [Mn12O12(O2CC6H4-p-Me)16(H2O)4].3(H2O) (7) crystallizes in the monoclinic space group I2/a, which at 223 K has a = 29.2794(4) A, b = 32.2371(4) A, c = 29.8738(6) A, beta = 99.2650(10) degrees, and Z = 8. The Mn12 molecules in complexes 6 and 7 differ in their arrangements of the four bound H2O ligands. Complex 6 exhibits an out-of-phase ac peak (chi(M)' ') in the 2-3 K region, whereas the hydrate complex 7 has a chi(M)' ' signal in the 4-7 K region. In addition, however, in complex 6, one Mn(III) ion has an abnormal Jahn-Teller distortion axis oriented at an oxide ion, and thus 6 and 7 are Jahn-Teller isomers. This reduces the symmetry of the core of complex 6 compared with complex 7. Thus, complex 6 likely has a larger tunneling matrix element and this explains why this complex shows a chi(M)' ' signal in the 2-3 K region, whereas complex 7 has its chi(M)' ' peak in the 4-7 K region, i.e., the rate of tunneling of magnetization is greater in complex 6 than complex 7. Detailed 1H NMR experiments (2-D COSY and TOCSY) lead to the assignment of all proton resonances for the benzoate and p-methyl-benzoate Mn12 complexes and confirm the structural integrity of the (Mn12O12) complexes upon dissolution. In solution there is rapi...