Strong-Acid-Catalyzed Formation of Crystalline LiNbO3 at Low Ambient Temperatures.

A crystalline LiNbO3 material was synthesized at 80 °C by an optimized sol-gel method using a double alkoxide alcoholic solution in the presence of hydrogen peroxide (H2O2) and strong acids. The same reaction in the presence of water or acetic acid resulted in amorphous powders with fewer impurities but which crystallized only at 450 °C and higher temperatures. The purity of the crystalline material obtained at 80 °C is strongly dependent on the Li/Nb molar ratio used for the reaction. It appears that the combination of strong acids with H2O2 in air generates perfect conditions for the synthesis of low-temperature crystalline lithium niobate oxide derivatives and can be extended to various other metal oxides. The developed synthetic method opens the potential for the coating of low-melting-point conductive polymer materials with LiNbO3 crystalline films.

Assisted Self-Assembly to Target Heterometallic Mn-Nd and Mn-Sm SMMs: Synthesis and Magnetic Characterisation of [Mn7 Ln3 (O)4 (OH)4 (mdea)3 (piv)9 (NO3 )3 ] (Ln=Nd, Sm, Eu, Gd)*.

In an assisted self-assembly approach starting from the [Mn6 O2 (piv)10 (4-Me-py)2 (pivH)2 ] cluster a family of Mn-Ln compounds (Ln=Pr-Yb) was synthesised. The reaction of [Mn6 O2 (piv)10 (4-Me-py)2 (pivH)2 ] (1) with N-methyldiethanolamine (mdeaH2 ) and Ln(NO3 )3 ⋅ 6H2 O in MeCN generally yields two main structure types: for Ln=Tb-Yb a previously reported Mn5 Ln4 motif is obtained, whereas for Ln=Pr-Eu a series of Mn7 Ln3 clusters is obtained. Within this series the GdIII analogue represents a special case because it shows both structural types as well as a third Mn2 Ln2 inverse butterfly motif. Variation in reaction conditions allows access to different structure types across the whole series. This prompts further studies into the reaction mechanism of this cluster assisted self-assembly approach. For the Mn7 Ln3 analogues reported here variable-temperature magnetic susceptibility measurements suggest that antiferromagnetic interactions between the spin carriers are dominant. Compounds incorporating Ln=NdIII (2), SmIII (3) and GdIII (5) display SMM behaviour. The slow relaxation of the magnetisation for these compounds was confirmed by ac measurements above 1.8 K.

Observation of electrochemically active Fe3+/Fe4+ in LiCo0.8Fe0.2MnO4 by in situ Mössbauer spectroscopy and X-ray absorption spectroscopy.

LiCo0.8Fe0.2MnO4 has been investigated as an active material for the positive electrode in lithium-ion batteries (LIBs) with a discharge potential of around 5 V (vs. Li+|Li). After synthesis by a Pechini based sol-gel route, the structural and morphological properties have been investigated by X-ray diffraction, scanning electron microscopy, 7Li MAS NMR spectroscopy, and 57Fe Mössbauer spectroscopy. With galvanostatic cycling, it was possible to obtain a specific discharge capacity of 117 mA h g-1, which is more than 80% of the theoretical capacity. The lithium extraction/insertion mechanism has been characterized by in situ synchrotron powder diffraction. The reversible oxidation process of Fe3+ to Fe4+ has been observed by in situ Mössbauer spectroscopy and in situ XAS measurements.

Field-Induced Co(II) Single-Ion Magnets with mer-Directing Ligands but Ambiguous Coordination Geometry.

Three air-stable Co(II) mononuclear complexes with different aromatic substituents have been prepared and structurally characterized by single-crystal X-ray diffraction. The mononuclear complexes [Co(H2L1)2]·2THF (1), [Co(HL2)2] (2), and [Co(H2L3)2]·CH2Cl2 (3) (where H3L1, H2L2, and H3L3 represent 3-hydroxy-naphthalene-2-carboxylic acid (6-hydroxymethyl-pyridin-2-ylmethylene) hydrazide, nicotinic acid (6-hydroxymethyl-pyridin-2-ylmethylene) hydrazide, and 2-hydroxy-benzoic acid (6-hydroxymethyl-pyridin-2-ylmethylene) hydrazide, respectively) feature a distorted mer octahedral coordination geometry. Detailed magnetic studies of 1-3 have been conducted using direct and alternating current magnetic susceptibility data. Field-induced slow magnetic relaxation was observed for these three complexes. There are few examples of such behavior in (distorted) octahedral coordination geometry (OC) Co(II) mononuclear complexes with uniaxial anisotropy. Analysis of the six-coordinate Co(II) mononuclear single-ion magnets (SIMs) in the literature using the SHAPE program revealed that they all show what is best described as distorted trigonal prismatic (TRP) coordination geometry, and in general, these show negative D zero-field splitting (ZFS) values. On the other hand, all the Co(II) mononuclear complexes displaying what is best approximated as distorted octahedral (OC) coordination geometry show positive D values. In the new Co(II) mononuclear complexes we describe here, there is an ambiguity, since the rigid tridentate ligands confer what is best described for an octahedral complex as a mer coordination geometry, but the actual shape of the first coordination sphere is between octahedral and trigonal prismatic. The negative D values observed experimentally and supported by high-level electronic structure calculations are thus in line with a trigonal prismatic geometry. However, a consideration of the rhombicity as indicated by the E value of the ZFS in conjunction with the SHAPE analysis shows that in this case it is difficult to distinguish between the OC and TRP descriptions.

A Three-Pronged Attack To Investigate the Electronic Structure of a Family of Ferromagnetic Fe4Ln2 Cyclic Coordination Clusters: A Combined Magnetic Susceptibility, High-Field/High-Frequency Electron Paramagnetic Resonance, and 57Fe Mössbauer Study.

We present the synthesis, structure, magnetic properties, as well as the Mössbauer and electron paramagnetic resonance studies of a ring-shaped [FeIII4LnIII2(Htea)4(µ-N3)4(N3)3(piv)3] (Ln = Y 1, Gd 2, Tb 3, Dy 4, Ho 5, Er, 6) coordination cluster. The Dy, Tb, and Ho analogues show blocking of the magnetization at low temperatures without applied fields. The anisotropy of the 3d ion and the exchange interaction between 3d and 4f ions in Fe4Ln2 complexes are unambiguously determined by high-field/high-frequency electron paramagnetic resonance measurements at low temperature. Ferromagnetic exchange interaction JFe-Ln is found which decreases upon variation of the Ln ions to larger atomic numbers. This dependence is similar to the behavior shown in the effective barrier values of complexes 3-5. Further information about the anisotropy of the Ln3+ ions was gathered with 57Fe Mössbauer spectroscopy, and the combination of these methods provides detailed information regarding the electronic structure of these complexes.

Search for Electron Delocalization from [Fe(CN)6]3- to the Dication of Viologen in (DNP)3[Fe(CN)6]2·10H2O.

K3Fe(CN)6 reacts with the viologen 1,1'-bis(2,4-dinitrophenyl)-4,4'-bipyridinium dication, (DNP)2+, to form a supramolecular complex, (DNP)3[Fe(CN)6]2·10H2O (1). The crystal structure of 1 reveals that there are two [Fe(CN)6]3- anions within an organic framework of three (DNP)2+ cations with the shortest Fe(III)···Fe(III) distances of ca. 9.8 Å, distances that minimize extensive long-range magnetic exchange coupling interactions between the [Fe(CN)6]3- anions, and, thus, 1 is paramagnetic above ca. 17 K and exhibits weak ferromagnetic coupling between 17 and 3 K and antiferromagnetic coupling between 3 and 1.8 K. The long Fe(III)···Fe(III) distances permit slow spin-spin and slow spin-lattice paramagnetic relaxation, relative to the iron-57 Larmor precession frequency, as is evidenced by the Mössbauer spectra measured between 3 and 60 K; between 85 and 295 K, rapid paramagnetic relaxation is observed. Both the slow spin-spin and slow spin-lattice relaxation are mediated by the organic, π-conjugated viologen cations. The Fe-C distances, the Mössbauer isomer shifts, the temperature dependence of the magnetic susceptibility, and the 3 K magnetization results all indicate the presence of low-spin Fe(III) ions in the [Fe(CN)6]3- anions in 1. There is no unequivocal indication of the presence of any formal electron delocalization or transfer from the [Fe(CN)6]3- anion to the (DNP)2+ cations in the results obtained from X-ray crystallography, magnetic measurements, and Mössbauer spectra. Because of enhancement of the spin-orbit coupling by the heavy-atom or -ion effect, the Fe(III) ions in the [Fe(CN)6]3- anions interact with the (DNP)2+ cations, causing them to fluoresce with increasing intensity upon cooling from 90 to 25 K when excited at 300 nm. The resulting luminescence of the viologen (DNP)2+ cation induced by the [Fe(CN)6]3- anions indicates the presence of significant mixing of the molecular orbitals derived from the [Fe(CN)6]3- anions and the molecular orbitals associated with the (DNP)2+ cations to yield bonding supramolecular orbitals in 1, a mixing that is also observed between 50 and 3 K in the temperature dependence of the isomer shift of 1.

Field-Induced Slow Magnetic Relaxation in the Ni(I) Complexes [NiCl(PPh3)2]·C4H8O and [Ni(N(SiMe3)2)(PPh3)2].

Direct current (dc) and alternating current (ac) magnetic measurements have been performed on the three Ni(I) complexes: [NiCl(PPh3)3], [NiCl(PPh3)2]·C4H8O, and [Ni(N(SiMe3)2)(PPh3)2]. Fits of the dc magnetic data suggest an almost similar behavior of the three compounds, which display only moderate deviations from the spin-only values. The ac magnetic investigations reveal that the two complexes with trigonal planar coordination--[NiCl(PPh3)2]·C4H8O and [Ni(N(SiMe3)2)(PPh3)2]--display slow magnetic relaxation at low temperatures under applied dc fields, whereas tetrahedral [NiCl(PPh3)3] does not. Ground and excited states as well as magnetic data were calculated by ab initio wave function based multi-configurational methods, including dynamic correlation as well as spin-orbit coupling. The two trigonal planar complexes comprise well-isolated S = (1)/2 ground states, whereas two S = (1)/2 states with a splitting of less than 100 cm(-1) were found in the tetrahedral compound.

Effect of Ligand Field Tuning on the SMM Behavior for Three Related Alkoxide-Bridged Dysprosium Dimers.

The synthesis and characterization of three Dy2 compounds, [Dy2(HL1)2(NO3)4] (1), [Dy2(L2)2(NO3)4] (2), and [Dy2(HL3)2(NO3)4] (3), formed using related tripodal ligands with a central tertiary amine bearing picolyl and alkoxy arms, 2-[(2-hydroxy-ethyl)-pyridin-2-ylmethylamino]-ethanol (H2L1), 2-(bis-pyridin-2-ylmethylamino)-ethanol (HL2), and 2-(bis-pyridin-2-ylmethylamino)-propane-1,3-diol (H2L3), are reported. The compounds are rare examples of alkoxide-bridged {Dy2} complexes and display capped square antiprism coordination geometry around each Dy(III) ion. Changes in the ligand field environment around the Dy(III) ions brought about through variations in the ligand donors can be gauged from the magnetic properties, with compounds 1 and 2 showing antiparallel coupling between the Dy(III) ions and 3 showing parallel coupling. Furthermore, slow relaxation of the magnetization typical of SMM behavior could be observed for compounds 2 and 3, suggesting that small variations in the ligand field can have a significant influence on the slow relaxation processes responsible for SMM behavior of Dy(III)-based systems.

Spin Helicity in Chiral Lanthanide Chains.

We report here the determination of the helical spin structure of three Ln-based chiral chains of the formula [Ln(Hnic)(nic)2(NO3)]n (Hnic = nicotinic acid; Ln = Tb, Dy, and Er) by means of cantilever torque magnetometry. While the Dy and Er derivatives are strongly axial (easy-axis and easy-plane anisotropy, respectively), the Tb derivative is characterized by a remarkable rhombicity. In agreement with these findings, alternating-current susceptibility reveals slow magnetic relaxation only in the Dy derivative. Dilution of DyIII ions in the diamagnetic Y-based analogue shows that the weak ferromagnetic intrachain interactions do not contribute significantly to the energy barrier for the reversal of magnetization, which is better described as a single-ion process. Single crystals of the two enantiomers of the Dy derivative have also been investigated using hard X-ray synchrotron radiation at the L-edge of the metal revealing optical activity although with negligible involvement of the 4f electrons of the DyIII ion.

Mixed-Valent Mn16-Containing Heteropolyanions: Tuning of Oxidation State and Associated Physicochemical Properties.

The two 16-manganese-containing, Keggin-based 36-tungsto-4-silicates [Mn(III)10Mn(II)6O6(OH)6(PO4)4(A-α-SiW9O34)4](28-) (1) and [Mn(III)4Mn(II)12(OH)12(PO4)4(A-α-SiW9O34)4](28-) (2) have been prepared by reaction of the trilacunary Keggin precursor [A-α-SiW9O34](10-) with either Mn(OOCCH3)3·2H2O (for 1) or MnCl2·4H2O (for 2), in aqueous phosphate solution at pH 9. Polyanions 1 and 2 comprise mixed-valent, cationic {Mn(III)10Mn(II)6O6(OH)6}(24+) and {Mn(III)4Mn(II)12(OH)12}(24+) cores, respectively, encapsulated by four phosphate groups and four {SiW9} units in a tetrahedral fashion. Both polyanions were structurally and compositionally characterized by single-crystal XRD, IR, thermogravimetric analysis, and X-ray absorption spectroscopy. Furthermore, studies were performed probing the magnetic, electrochemical, oxidation catalytic, and Li-ion battery performance of 1 and 2.

Multiple superhyperfine fields in a {DyFe2Dy} coordination cluster revealed using bulk susceptibility and (57)Fe Mössbauer studies.

A [DyFeDy(µ3-OH)2(pmide)2(p-Me-PhCO2)6] coordination cluster, where pmideH2 = N-(2-pyridylmethyl)iminodiethanol, has been synthesized and the magnetic properties studied. The dc magnetic measurements reveal dominant antiferromagnetic interactions between the metal centres. The ac measurements reveal zero-field quantum tunnelling of the magnetisation (QTM) which can be understood, but not adequately modelled, in terms of at least three relaxation processes when appropriate static (dc) fields are applied. To investigate this further, (57)Fe Mössbauer spectroscopy was used and well-resolved nuclear hyperfine structures could be observed, showing that on the Mössbauer time scale, without applied field or else with very small applied fields, the iron nuclei experience three or more superhyperfine fields arising from the slow magnetisation reversal of the strongly polarized fields of the Dy(III) ions.

Magnetic anisotropy of a CoII single ion magnet with distorted trigonal prismatic coordination: theory and experiment.

The single ion magnetic properties of Co(ii) are affected by the details of the coordination geometry of the ion. Here we show that a geometry close to trigonal prismatic which arises when the ligand 6,6'-((1Z)-((piperazine-1,4-diylbis(propane-3,1-diyl))bis(azanylylidene))bis(methanylylidene))bis(2-methoxyphenol) coordinates to Co(ii) does indeed lead to enhanced single-ion behaviour as has previously been predicted. Synthesis of the compound, structural information, and static as well as dynamic magnetic data are presented along with an analysis using quantum chemical ab initio calculations. Though the complex shows a slight deviation from an ideal trigonal prismatic coordination, the zero-field splitting as well as the g-tensor are strongly axial with D = -41 cm-1 and E < 0.01 cm-1. For the lowest Kramers doublet (S = 1/2) g∥ = 7.86 and g⊥ < 0.05 were found. In contrast, the second Kramers doublet possesses a rhombic g-tensor with g∥ = 2.75 and g⊥ = 4.35. Due to large spin-orbit coupling resulting in very different g tensors, it is not possible to simulate the temperature dependence of the magnetic susceptibility with a spin Hamiltonian of the form H = D(Sz2 - S(S + 1)/3) + E(Sx2 - Sy2) + µBgS·B using an effective spin S = 3/2. Calculations on model complexes show the influence of the coordinating atoms and the deviation from the ideal trigonal prismatic coordination. As the distortion is reduced towards idealised D3h, the zero field splitting increases and the g-tensor of the second Kramers doublet also becomes axial.

A Strongly Spin-Frustrated Fe(III) 7 Complex with a Canted Intermediate Spin Ground State of S=7/2 or 9/2.

A disk-shaped [Fe(III) 7 (Cl)(MeOH)6 (µ3 -O)3 (µ-OMe)6 (PhCO2 )6 ]Cl2 complex with C3 symmetry has been synthesised and characterised. The central tetrahedral Fe(III) is 0.733 Šabove the almost co-planar Fe(III) 6 wheel, to which it is connected through three µ3 -oxide bridges. For this iron-oxo core, the magnetic susceptibility analysis proposed a Heisenberg-Dirac-van Vleck (HDvV) mechanism that leads to an intermediate spin ground state of S=7/2 or 9/2. Within either of these ground state manifolds it is reasonable to expect spin frustration effects. The (57) Fe Mössbauer (MS) analysis verifies that the central Fe(III) ion easily aligns its magnetic moment antiparallel to the externally applied field direction, whereas the other six peripheral Fe(III) ions keep their moments almost perpendicular to the field at stronger fields. This unusual canted spin structure reflects spin frustration. The small linewidths in the magnetic Mössbauer spectra of polycrystalline samples clearly suggest an isotropic exchange mechanism for realisation of this peculiar spin topology.

Developing a "highway code" to steer the structural and electronic properties of Fe(III)/Dy(III) coordination clusters.

In the recently established field of 3d/4f coordination cluster (CC) chemistry several burning questions still need to be addressed. It is clear that combining 3d and 4f metal ions within a coordination cluster core has the potential to lead to electronic structures that will be very difficult to describe but can also be extremely interesting. Furthermore, understanding why certain core topologies seem to be favored is difficult to predict. Here we show that the secondary coordination sphere provided by the ligands influences the favored product, as demonstrated for the compound [Fe4Dy2(µ3-OH)2(n-bdea)4(C6H5CO2)8]·MeCN (1), which has a 2Fe:2Dy:2Fe core and was made using [Fe(III)3O(C6H5)CO2)(L)3](+) as starting material plus Dy(NO3)3 and N-n-butyl-diethanolamine (n-bdeaH2), compared with the compound made using a methyl meta-substituent (R) on the phenyl ring of the benzoate, [Fe(III)3O(C6H4Me)CO2)(L)3](+) as starting material, which resulted in the "square-in-square" compound [Fe4Dy4(µ3-OH)4(n-bdea)4(O2CC6H4CH3)12]·MeCN (2) when using ambient conditions. Changing reaction conditions from ambient to solvothermal leads to "double-propeller" compounds [Fe4Dy4(µ4-O)3(n-bdea)3(C6H5CO2)12]·13MeCN (3) and [Fe4Dy4(µ4-O)3(n-bdea)3(O2CC6H4CH3)12]·MeCN (4) forming with this core, resulting irrespective of the substitution on the iron benzoate starting material. Furthermore, compounds 1 and 2 can be transformed into compounds 3 and 4, respectively, using a solvothermal method. Thus, compounds 3 and 4 appear to be the thermodynamically most stable species. The factors steering the reactions toward these products are discussed. The electronic structures have been investigated using magnetic and Mössbauer studies. All compounds are cooperatively coupled 3d/4f systems, with compound 1 showing single-molecule magnet behavior.

Mononuclear and tetranuclear compounds of yttrium and dysprosium ligated by a salicylic schiff-base derivative: synthesis, photoluminescence, and magnetism.

The Schiff-base (2-aminoethyl)hydroxybenzoic acid (H(2)L) as a proligand was prepared in situ from 3-formylsalicylic acid and ethanolamine (ETA). The mononuclear {[Y(HL)(4)][ETAH]·H(2)O} (1) and {[Dy(HL)(4)] [ETAH]·3MeOH·H(2)O} (2) and tetranuclear {[Y(4)(HL)(2)(L)(4)(µ(3)-OH)(2)]·4MeOH·4H(2)O} (3), {[Dy4(HL)(2)(L)(4)(µ(3)-OH)(2)]·5(MeOH)(2)·7H(2)O (4), and {[Dy(4)(HL)(8)(L)(2)]·4MeOH·(2)H(2)O}(5) rare-earth metal complexes of this ligand could be obtained as single-crystalline materials by the treatment of H(2)L in the presence of the metal salts [Ln(NO(3))(3)·(H(2)O)m] (Ln = Y, Dy). In the solid state, the tetranuclear compounds 3 and 4 exhibit butterfly structures, whereas 5 adopts a rectangular arrangement. Electrospray ionization mass spectrometry data of the ionic compounds 1 and 2 support single-crystal X-ray analysis. The yttrium compounds 1 and 3 show fluorescence with 11.5% and 13% quantum yield, respectively, whereas the quantum yield of the dysprosium complex 4 is low. Magnetic studies on the dysprosium compounds 4 and 5 suggest the presence of weak antiferromagnetic interactions between neighboring metal centers. Compound 4 shows single-molecule-magnet behavior with two relaxation processes, one with the effective energy barrier U(eff) = 84 K and the preexponential factor τ(0) = 5.1 × 10(-9) s.

Tetranuclear and Pentanuclear Compounds of the Rare-Earth Metals: Synthesis and Magnetism.

The Schiff-base proligand 4-tert-butyl-2,6-bis-[(2-hydroxy-phenylimino)methyl]phenol (H3L) was prepared in situ from 4-tert-butyl-2,6-diformylphenol and 2-aminophenol. The proligand (H3L) was used with dibenzoylmethane (DBMH) or acetylacetone (acacH) with lanthanides giving compounds with varying arrangements of metal atoms and nuclearities. The tetranuclear compound {[Dy4(L)3(DBM)4][Et3NH]} (1) and pentanuclear compound {[Dy5(µ3-OH)2(L)3(DBM)4(MeOH)4]·4(MeOH)} (2) were obtained from the ligand (L)(3-) and dibenzoylmethane. The tetranuclear compounds {[Dy4(µ4-OH)(L)2(acac)4(MeOH)2(EtOH)(H2O)]·(NO3)·2(MeOH)·3(EtOH)} (3) and {[Ln4(µ3-OH)2(L)(HL)(acac)5(H2O)] (HNEt3)(NO3)·2(Et2O)} (Ln = Tb (4), Dy (5), Ho (6), and Tm (7)) resulted when the ligand (L)(3-) was used in the presence of acetylacetone. In the solid state structures, the tetranuclear compound 1 adopts a linear arrangement of metal atoms, while tetranuclear compound 3 has a square grid arrangement of metal atoms, and tetranuclear compounds 4-7 have a seesaw-shaped arrangement of metal atoms. The composition found from single-crystal X-ray analysis of compound 1 and 3-7 is supported by electrospray ionization mass spectrometry (ESI-MS). The magnetic studies on compounds 1 suggest the presence of weak ferromagnetic interactions, whereas compounds 2-6 exhibit weak antiferromagnetic interactions between neighboring metal centers. Compounds 1, 2, and 3 also show single-molecule magnet behavior under an applied dc field.

An Approach to More Accurate Model Systems for Purple Acid Phosphatases (PAPs).

The active site of mammalian purple acid phosphatases (PAPs) have a dinuclear iron site in two accessible oxidation states (Fe(III)2 and Fe(III)Fe(II)), and the heterovalent is the active form, involved in the regulation of phosphate and phosphorylated metabolite levels in a wide range of organisms. Therefore, two sites with different coordination geometries to stabilize the heterovalent active form and, in addition, with hydrogen bond donors to enable the fixation of the substrate and release of the product, are believed to be required for catalytically competent model systems. Two ligands and their dinuclear iron complexes have been studied in detail. The solid-state structures and properties, studied by X-ray crystallography, magnetism, and Mössbauer spectroscopy, and the solution structural and electronic properties, investigated by mass spectrometry, electronic, nuclear magnetic resonance (NMR), electron paramagnetic resonance (EPR), and Mössbauer spectroscopies and electrochemistry, are discussed in detail in order to understand the structures and relative stabilities in solution. In particular, with one of the ligands, a heterovalent Fe(III)Fe(II) species has been produced by chemical oxidation of the Fe(II)2 precursor. The phosphatase reactivities of the complexes, in particular, also of the heterovalent complex, are reported. These studies include pH-dependent as well as substrate concentration dependent studies, leading to pH profiles, catalytic efficiencies and turnover numbers, and indicate that the heterovalent diiron complex discussed here is an accurate PAP model system.

Tetradecanuclear Iron(III)-Oxo Nanoclusters Stabilized by Trilacunary Heteropolyanions.

The tetrameric, multi-Fe(III)-containing polyoxotungstates [Fe14O6(OH)13(P2W15O56)4](31-) (1) and [Na2Fe14(OH)12(PO4)4(A-α-XW9O34)4](20-) (X = Si(IV) (2), Ge(IV) (3)) have been successfully synthesized under conventional reaction conditions in aqueous, slightly acidic (1), or basic (2 and 3) media. Polyanions 1-3 were characterized in the solid state by single-crystal X-ray diffraction, IR spectroscopy, thermogravimetric analysis, and magnetic studies, and in solution by electrochemistry.

Self-Assembly of a Giant Tetrahedral 3 d-4 f Single-Molecule Magnet within a Polyoxometalate System.

A giant tetrahedral heterometallic polyoxometalate (POM) [Dy30 Co8 Ge12 W108 O408 (OH)42 (OH2 )30 ](56-) , which shows single-molecule magnet (SMM) behavior, is described. This hybrid contains the largest number of 4f ions of any polyoxometalate (POM) reported to date and is the first to incorporate two different 3d-4f and 4f coordination cluster assemblies within same POM framework.

Enhancement of spin relaxation in an FeDy2 Fe coordination cluster by magnetic fields.

Two [FeLn2 Fe(µ3 -OH)2 (teg)2 (N3 )2 (C6 H5 COO)4 ] compounds (where Ln=Y(III) and Dy(III) ; teg=triethylene glycol anion) have been synthesized and studied using SQUID and Mössbauer spectroscopy. The magnetic measurements on both compounds indicate dominant antiferromagnetic interactions between the metal centers. Analysis of the (57) Fe Mössbauer spectra complement the ac magnetic susceptibility measurements, which show how a static magnetic field can quench the slow relaxation of magnetization generated by the anisotropic Dy(III) ions.