Mixing it up: A ground spin state of S=83/2 is found in the mixed-valent manganese aggregate [MnIII12MnII7(μ4-O)8(μ3,η1-N3)8(HL)12(MeCN)6]2+ (H3L=2,6-bis(hydroxymethyl)-4-methylphenol; see polyhedral representation core) and arises through ferromagnetic coupling all metal centers. Supporting information for this article available on WWW under http://www.wiley-vch.de/contents/jc_2002/2006/z601467_s.pdf or from author. Please note: The publisher not responsible content functionality any...

The tridecanuclear heterovalent mixed-metal (Mn11Gd2) complex [MnIII9MnII2GdIII2(O)8(OH)2(O2CR)17(NO3)2(H2O)] has been obtained from the reaction of hexanuclear compound [Mn6O2(Piv)10(4-Me-py)2.5(PivH)1.5] with Gd(NO3)3·6H2O in CH3CN. presents an unusual "bell"-shaped core a high-spin ground state and is new member high-nuclearity 3d-4f single-molecule magnets family.

A record anisotropy barrier (319 cm(-1) ) for all d-f complexes was observed a unique Fe(II) -Dy(III) -Fe(II) single-molecule magnet (SMM), which possesses two asymmetric and distorted ions one quasi-D5h Dy(III) ion. The frozen magnetization of the ion leads to decreased relaxation rates evident in Mössbauer spectrum. Ab initio calculations suggest that tunneling is interrupted effectively thanks exchange doublets.

Abstract LiNi 0.5 Mn 1.5 O 4 (LNMO) cathode active materials for lithium‐ion batteries have been investigated over 20 years. Despite all this effort, it has not possible to transfer their favorable properties into applicable, stable battery cells. To make further progress, the research perspective on these spinel type needs be updated and a number of persisting misconceptions LNMO overcome. Therefore, current knowledge is summarized controversial points are addressed by detailed...

The reaction of [Mn6O2(Piv)(10)(4-Me-py)(2.5)(PivH)(1.5)] (1) (py: pyridine, Piv: pivilate) with N-methyldiethanolamine (mdeaH2) and Ln(NO3)3 x 6 H2O in MeCN leads to a series nonanuclear compounds [Mn5Ln4(O)6(mdea)2(mdeaH)2(Piv)6(NO3)4(H2O)2]2 (Ln=Tb(III) (2), Dy(III) (3), Ho(III) (4), Y(III) (5)). Single-crystal X-ray diffraction shows that 2-5 are isostructural, the central core composed two distorted {Mn(IV)Mn(III)Ln2O4} cubanes sharing Mn(IV) vertex, representing new heterometallic...

Anisotropy can be introduced into the [Mn(19)]-aggregate, which currently has highest known spin ground state of S = 83/2, by targeted replacement central Mn(II) cation with Dy(III) leading to a [Mn(18)Dy] complex same core topology showing slow relaxation magnetisation.

Alternating current magnetic investigations on the trigonal-planar high-spin Co(2+) complexes [Li(15-crown-5)] [Co{N(SiMe3)2}3], [Co{N(SiMe3)2}2(THF)] (THF = tetrahydrofuran), and [Co{N(SiMe3)2}2(PCy3)] (Cy -C6H13 cyclohexyl) reveal that all three display slow relaxation at temperatures below 8 K under applied dc (direct current) fields. The parameters characteristic for their respective processes such as effective energy barriers Ueff (16.1(2), 17.1(3), 19.1(7) cm(-1)) times τ0 (3.5(3) ×...

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 any reported to date and first incorporate two different 3d-4f coordination cluster assemblies within same POM framework.

Ferromagnetic interactions in an Fe4Dy4 single-molecule magnet were studied using a combination of magnetic susceptibility measurements (see diagram; inset: cluster core) and 57Fe Mössbauer spectroscopy.

Gut gemischt: Ein Grundzustandsspin von S=83/2 wurde für das gemischtvalente Manganaggregat [MnIII12MnII7(μ4-O)8(μ3,η1-N3)8(HL)12(MeCN)6]2+ nachgewiesen (H3L=2,6-Bis(hydroxymethyl)-4-methylphenol; der Kern ist in Polyederdarstellung gezeigt). Die Größe des Spins darauf zurückzuführen, dass alle Metallzentren ferromagnetisch koppeln. Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2001/2006/z601467_s.pdf or from author. Please note:...

Stepping up: A two-step magnetic spin transition with accompanying structural phase transitions is reported for the first time FeIII. The are observed at 187 K and 90 on cooling a hysteretic recorded upon heating during crossover 106 K. intermediate persists over 97 contains an unprecedented [HS-HS-LS] motif tripling of unit cell.

The reaction between N-methydiethanolamine (mdeaH(2)), benzoic acid, FeCl(3), and DyCl(3) yields a decanuclear coordination cluster, [Dy(3)Fe(7)(mu(4)-O)(2)(mu(3)-OH)(2)(mdea)(7)(mu-benzoate)(4)(N(3))(6)] x 2 H(2)O 7 CH(3)OH (1) whose single crystal structure exhibits three seven crystallographically distinct Dy(III) Fe(III) ions; six of the ions are pseudo-octahedrally coordinated, whereas seventh has trigonal-bipyramidal geometry. Both direct current (dc) alternating (ac) magnetic...

A great combination: The large uniaxial anisotropy of lanthanides and its influence on the local moments spin-relaxation dynamics at iron nuclei was probed by using 57Fe Mössbauer spectroscopy magnetic susceptibility measurements (see picture). derivation possible comparing isomorphous clusters containing diamagnetic, isotropic, anisotropic lanthanide ions. Detailed facts importance to specialist readers are published as "Supporting Information". Such documents peer-reviewed, but not...

The reaction of triethanolamine (teaH3) with [FeIII3O(O2CCH3)6(H2O)3]Cl·6H2O and Ln(NO3)3·6H2O in acetonitrile yields [Fe16Ln4(tea)8(teaH)12(μ-O2CCH3)8](NO3)4·16H2O·xMeCN (Ln = Sm (1), Eu (2), Gd (3), Tb (4), Dy (5), Ho (6); x 10 or 11). These 20-membered metallo-ring complexes are the largest such single-stranded oxygen-bridged rings so far reported. structure is stabilised by two acetate ligands, which form anti,anti-bridges across centre ring, pinching ring giving it rigidity. magnetic...

A series of [Fe(2)Dy(2)(OH)(2)(teaH)(2)(RC(6)H(4)COO)(6)] compounds has been synthesized and studied using Mössbauer spectroscopy. It is suggested that the local crystal field Dy(III) centers external magnetic can control their shape anisotropy thus interactions between dysprosium iron centers.

Synthesis, structure, magnetism and photophysical properties of a series homodinuclear lanthanide complexes are reported.

Direct current (dc) and alternating (ac) magnetic measurements have been performed on the three Ni(I) complexes: [NiCl(PPh3)3], [NiCl(PPh3)2]·C4H8O, [Ni(N(SiMe3)2)(PPh3)2]. Fits of dc data suggest an almost similar behavior compounds, which display only moderate deviations from spin-only values. The ac investigations reveal that two complexes with trigonal planar coordination—[NiCl(PPh3)2]·C4H8O [Ni(N(SiMe3)2)(PPh3)2]—display slow relaxation at low temperatures under applied fields, whereas...

The synthesis and characterization of three Dy2 compounds, [Dy2(HL1)2(NO3)4] (1), [Dy2(L2)2(NO3)4] (2), [Dy2(HL3)2(NO3)4] (3), formed using related tripodal ligands with a central tertiary amine bearing picolyl alkoxy arms, 2-[(2-hydroxy-ethyl)-pyridin-2-ylmethylamino]-ethanol (H2L1), 2-(bis-pyridin-2-ylmethylamino)-ethanol (HL2), 2-(bis-pyridin-2-ylmethylamino)-propane-1,3-diol (H2L3), are reported. compounds rare examples alkoxide-bridged {Dy2} complexes display capped square antiprism...

The single-ion magnetic properties of a trigonal-prismatic Co(<sc>ii</sc>) complex (left) are explored experimentally as well analysed with respect to the coordination geometry by quantum chemical <italic>ab initio</italic> methods.

Tuning of relaxation magnetisation through 3d metal ion variations in 3d₂Dy₂ butterflies.

Three isostructural disklike heptanuclear FeIII compounds of the general formula [FeIII7(μ3-O)3(L)3(μ-O2CCMe3)6(η1-O2CCMe3)3(H2O)3], where L represents a di- or triethanolamine moiety, display three-blade propeller topology, with central Fe atom representing axle axis propeller. This motif corresponds to theoretical model frustrated Heisenberg star, which is one very few solvable models in area quantum-spin systems and can, furthermore, be converted an octanuclear cage for case give...

A series of heterometallic complexes formula [Mn(III)(2)Ln(III)(3)(bdeaH)(3)(bdea)(2)(piv)(8)] x MeCN, where bdeaH(2) = N-butyldiethanolamine, piv pivalate, and Ln Y (1), Tb (2), Dy (3), Ho (4), Er (5), has been prepared. 1-5 are isostructural, with the metal centers forming a novel semicircular Ln(III)-Mn(III)-Ln(III)-Mn(III)-Ln(III) strand. Only 2 3 exhibit slow relaxation magnetization, suggesting that highly anisotropic Ln(III) ions (Tb(III) Dy(III)) essential for an energy barrier to...

The structures and magnetic properties of a family new octanuclear heterometallic 3d-4f complexes [MnIII4LnIII4(μ3-OH)4(μ2,η1-X)4(O2CBut)8(t-bdea)4]·solv, where X = N3−, Ln Y (1), Eu (2), Gd (3), Tb (4), Dy (5), Ho (6); OCN−, (7); NO3−, (8), (9), (10), (11), Er (12); solv MeCN or toluene, are reported. metal topology in the aggregates can be described as consisting "Ln4-square inscribed Mn4-square". Complexes 1-7 prepared by reactions t-butyldiethanolamine (t-bdeaH2) with preformed...

A pi-extended, redox-active tetradentate tetrathiafulvalene-fused salphen [salphen = N,N'-phenylenebis(salicylideneimine)] compound (L) was prepared via a direct Schiff-base condensation of the corresponding diamine-tetrathiafulvalene (TTF) precursor with salicylaldehyde. Its chelating coordination ability has been demonstrated by formation transition metal complexes in presence M(OAc)2.nH2O (M Co(II), Ni(II), Cu(II)) and FeCl3.6H2O. Three have characterized single-crystal X-ray diffraction...

Abstract Reactions of Ce III (NO 3 ) ⋅6 H 2 O or (NH 4 [Ce IV 6 ] with Mn‐containing starting materials result in seven novel polynuclear Ce/Mn complexes pivalato ( t BuCO $\rm{{_{2}^{-}}}$ and, most cases, auxiliary N,O‐ N,O,O‐donor ligands. With nuclearities ranging from 6–14, the compounds present aesthetically pleasing structures. Complexes μ ‐O) ‐OH) ‐O C Bu) 12 1 ), Mn (O (ea) (OAc) ]⋅4 O⋅4 MeCN (ea − =2‐aminoethanolato; 8 (pye) 18 10 5 (H O)]⋅21 (pye =pyridine‐2‐ethanolato; and bdea)...