1-D coordination polymers consisting of a high-spin Mn17 octahedral unit

The reaction of [Mn(O₂CMe)₂] · 4H₂O with pdH₂ (1,3-propanediol) or mpdH₂ (2-methyl-1,3-propanediol) in the presence of NaN₃ in MeCN/py (py = pyridine) results in the formation of two new one-dimensional coordination polymers composed of a [Mn^III₆Mn^II₁₁(μ₄-O)₈(μ₃-N₃)₄]²⁵⁺ octahedral unit. The peripheral ligation is completed by pd^2? (or mpd^2?), acetate, pyridine and μ-1,3-N₃^? ligands. The latter bridges each Mn₁₇ unit to its neighboring one, resulting in the formation of the two 1-D coordination polymers. Variable-temperature dc magnetic susceptibility studies indicate the existence of predominantly ferromagnetic interactions and a resulting giant ground state spin within the Mn₁₇ units and intermolecular antiferromagnetic exchange interactions between the neighboring Mn₁₇ units that result in diamagnetic ground spin states for both polymeric compounds.     

A large [Mn10Na]4 loop of four linked Mn10 loops

A large [Mn10Na]4 loop-of-loops aggregate was prepared from the use of 1,3-propanediol (pdH2) in manganese carboxylate chemistry. It is constructed from four [Mn10(mu3-O)2(O2CMe)13(pd)6(py)2]- loops linked through Na+ ions and exhibits a saddlelike topology. Magnetic characterization showed that the Mn10 loop has an S approximately 4 ground-state spin and displays frequency-dependent in-phase and out-of-phase alternating current signals and also hysteresis loops that, however, are not typical of single-molecule magnets because of the existence of intermolecular interactions between the Mn10 units.     

Single-molecule magnets: a family of MnIII/CeIV complexes with a [Mn8CeO8]12+ core

Four heterometallic, enneanuclear Mn8Ce clusters [Mn8CeO8(O2CMe)12(H2O)4] (4), [Mn8CeO8(O2CMe)12(py)4] (5), [Mn8CeO8(O2CPh)12(MeCN)4] [Mn8CeO8(O2CPh)12(dioxane)4] (6), and [Mn8CeO8(O2CCHPh2)12(H2O)4] (7) have been prepared by various methods. Their cores are essentially isostructural and comprise a nonplanar, saddlelike [MnIII8O8]8+ loop containing a central CeIV ion attached to the eight micro3-O2- ions. Peripheral ligation around the [Mn8CeO8]12+ core is provided by eight micro- and four micro3-O2CR- groups. Terminal ligation on four MnIII atoms is provided by H2O in 4 and 7, pyridine in 5, and MeCN/dioxane in 6. Solid-state magnetic susceptibility studies, fits of dc magnetization vs field and temperature data, and in-phase ac susceptibility studies in a zero dc field have established that complexes 4, 5, and 7 possess S=16, S=4 or 5, and S=6+/-1 spin ground states, respectively, but in all cases there are very low-lying excited states. The large variation in the ground-state spins for this isostructural family is rationalized as due to a combination of weak exchange interactions between the constituent MnIII atoms, and the presence of both nearest-neighbor and next-nearest-interactions of comparable magnitudes. Magnetization vs applied dc field sweeps on single crystals of 4.4H2O and 7.4H2O.3MeCN.2CH2Cl2 down to 0.04 K have established that these two complexes are new single-molecule magnets (SMMs). The former also shows an exchange-bias, a perturbation of its single-molecule properties from very weak intermolecular interactions mediated by hydrogen-bonding interactions with lattice-water molecules of crystallization.     

A new family of octanuclear Mn complexes with a rod-like topology

Three new octanuclear compounds were prepared from reactions of [Mn(O₂CR)₂]·2H₂O (R = Et or Ph) with the diols 1,3-propanediol (pdH₂) or 2-methyl-1,3-propanediol (mpdH₂) in the presence of NaN₃. All three compounds [Mn₈(N₃)₄(O₂CR)₆(L)₄(py)₆] (L = pd²⁻, R = Et 1; L = mpd²⁻, R = Et 2; L = pd²⁻, R = Ph 3) (py = pyridine) possess a novel near-planar, rod-like topology. Dc and ac magnetic susceptibility studies in the 2–300 K range for complexes 1 and 2 revealed the presence of dominant antiferromagnetic exchange interactions, leading to diamagnetic ground spin states.     

A Mn36Ni4 'loop-of-loops-and-supertetrahedra' aggregate possessing a high S(T) = 26 ± 1 spin ground state

The initial use of 1,3-propanediol in mixed Mn/3d cluster chemistry has led to a Mn(III)(28)Mn(II)(8)Ni(II)(4) molecular aggregate which consists of two Mn(III)(8)Ni(2) loops and two Mn(III)(6)Mn(II)(4) supertetrahedral units and displays a high ground spin state value S(T) = 26 ± 1.     

One-pot regioselective synthesis and X-ray crystal structure of a stable [60]fullerene trisadduct with the e(edge),e(face),trans-1 addition pattern

The Bingel functionalisation of C(60) with a structurally novel tether equipped with three reactive malonate groups afforded a C(2v)-symmetrical e(edge),e(face),trans-1 trisadduct in a complete regioselective manner and in an excellent yield of 65%. The [60]fullerene trisadduct showed pronounced ability to crystallise and gave X-ray quality single crystals for analysis.     

High nuclearity single-molecule magnets: a mixed-valence Mn26 cluster containing the di-2-pyridylketone diolate dianion

The employment of the dianion (dpkd(2-)) of the gem-diol form of di-2-pyridylketone (dpk) as a tetradentate chelate in manganese chemistry is reported, and the synthesis, crystal structure, and magnetochemical characterization of [Mn26O16(OMe)12(dpkd)12(MeOH)6](OH)6 x solv (3 x solv) are described. The reaction of Mn(ClO4)2 x 6 H2O, dpk, NaOMe, and NEt3 (2:1:4:2) in MeCN/MeOH affords complex 3, which possesses a rare metal topology and is mixed-valence (4 Mn(II), 22 Mn(III)). The complicated [Mn26(mu4-O)10(mu3-O)6(mu3-OMe)12(mu-OR)12](18+) core of 3 consists of an internal Mn(III)16 cage of adjacent Mn4 tetrahedra surrounded by an external Mn(II)4Mn(III)6 shell. The latter is held together by the alkoxide arms of twelve eta(1):eta(2):eta(1):eta(1):mu3 dpkd(2-) groups. Variable-temperature, solid-state direct current (dc), and alternating current (ac) magnetization studies were carried out on 3 in the 1.8-300 K range. Complex 3 is predominantly antiferromagnetically coupled with a resulting S = 6 ground state, a conclusion confirmed by the in-phase (chi'(M)) ac susceptibility data. The observation of out-of-phase (chi'(M)) ac susceptibility signals suggested that 3 might be a single-molecule magnet, and this was confirmed by single-crystal magnetization vs dc field sweeps that exhibited hysteresis, the diagnostic property of a magnet. Combined ac chi'(M) and magnetization decay vs time data collected below 1.1 K were used to construct an Arrhenius plot; the fit of the thermally activated region above approximately 0.1 K gave U(eff) = 30 K, where U(eff) is the effective relaxation barrier. At lower temperatures, the complex exhibits temperature-independent relaxation, characteristic of ground-state quantum tunneling of magnetization between the lowest-lying M(s) = +/-6 levels. The combined work demonstrates the ligating flexibility of dipyridyl-diolate chelates and their usefulness in the synthesis of polynuclear Mn(x) clusters with interesting magnetic properties, without requiring the co-presence of carboxylate ligands.