A spin-frustrated star-shaped heterotetranuclear CrIIIMnII3 species and its magnetic and HF-EPR measurements.

A tetranuclear complex [Cr(III)Mn(II)(3)(PyA)(6)Cl(3)] 1 containing pyridine-2-aldoximato monoanion, PyA, has been structurally and magnetochemically characterized. The compound is a rare example of a tetranuclear star-shaped metal topology containing pyridine-2-aldoximato ligands. Static magnetic studies have demonstrated very weak antiferromagnetic exchange interactions between the paramagnetic centers (S(Cr) = 3/2 and S(Mn) = 5/2) resulting in closely spaced low-lying levels, which undergo splitting and crossing. Preliminary high-field EPR measurements (20 < nu < 388 GHz) indicate the presence of zero-field splitting D of the order of 0.7 cm(-1).

[1]  E. Bill,et al.  Deliberate synthesis for magnetostructural study of linear tetranuclear complexes BIIIMnIIMnIIBIII, MnIIIMnIIMnIIMnIII, MnIVMnIIMnIIMnIV, FeIIIMnIIMnIIFeIII, and CrIIIMnIIMnIICrIII. Influence of terminal ions on the exchange coupling. , 2006, Inorganic chemistry.

[2]  A. Postnikov,et al.  The {FeIII[FeIII(L1)2]3} star-type single-molecule magnet , 2006 .

[3]  M. Goiran,et al.  Tuning the magnetic ground state of a tetranuclear nickel(II) molecular complex by high magnetic fields , 2006, cond-mat/0601102.

[4]  T. Weyhermüller,et al.  Self-assembly of a nonanuclear nickel(II) complex and its magnetic properties. , 2005, Inorganic chemistry.

[5]  Song Gao,et al.  Rational synthesis and magnetic properties of a family of low-dimensional heterometallic Cr-Mn complexes based on the versatile building block [Cr(2,2'-bipyridine)(CN)4]-. , 2005, Inorganic chemistry.

[6]  Chunhua Yan,et al.  Tetramanganese(II) cluster with centered trigonal topology: structure and magnetic properties. , 2005, Inorganic chemistry.

[7]  A. Neels,et al.  Cyano-bridged structures based on [MnIIN3O2-macrocycle)]2+: a synthetic, structural, and magnetic study. , 2005, Inorganic chemistry.

[8]  V. Kravtsov,et al.  Oxalato‐Bridged [CuIICrIII] and [MnIICrIII] Binuclear Complexes: Synthesis, Crystal Structures, Magnetic and EPR Investigations , 2004 .

[9]  K. Wieghardt,et al.  Asymmetric Heterodinuclear FeIIIMII (M = Zn, Cu, Ni, Fe, Mn), CoIIIFeII and FeIICoIII Species: Synthesis, Structure, Redox Behavior, and Magnetism , 2004 .

[10]  P. Chaudhuri Homo- and hetero-polymetallic exchange coupled metal-oximates , 2003 .

[11]  R. Sessoli,et al.  Quantum tunneling of magnetization and related phenomena in molecular materials. , 2003, Angewandte Chemie.

[12]  A. Rompel,et al.  A Tetranuclear Manganese Cluster with a Star-Shaped Mn4O6 Core Motif: Directed Synthesis using a Mononuclear Precursor Complex† , 2002 .

[13]  K. Wieghardt,et al.  Polynuclear complexes of the pendent-arm ligand 1,4,7-tris(acetophenoneoxime)-1,4,7-triazacyclononane. , 2002, Inorganic chemistry.

[14]  R. Schenker,et al.  Competing interactions in the tetranuclear spin cluster [Ni[(OH)(2)Cr(bispictn)](3)]I(5).5H(2)O. An inelastic neutron scattering and magnetic study. , 2002, Inorganic chemistry.

[15]  X. Bu,et al.  First tetrameric NiII cluster with planar triangular topology exhibiting ferromagnetic pathways. , 2002, Chemical communications.

[16]  K. Wieghardt,et al.  Tris(pyridinealdoximato)metal complexes as ligands for the synthesis of asymmetric heterodinuclear Cr(III)M species [M = Zn(II), Cu(II), Ni(II), Fe(II), Mn(II), Cr(II), Co(III)]: a magneto-structural study. , 2001, Inorganic chemistry.

[17]  G. Vaughan,et al.  Ligand-to-metal ratio controlled assembly of tetra- and hexanuclear clusters towards single-molecule magnets. , 2001, Chemistry.

[18]  J. Long,et al.  Manganese–Chromium–Cyanide Clusters: Molecular MnCr6(CN)18 and Mn3Cr6(CN)18 Species and a Related MnCr3(CN)9 Chain Compound , 2001 .

[19]  R. Winpenny High-nuclearity paramagnetic 3d-metal complexes with oxygen- and nitrogen-donor ligands , 2001 .

[20]  D. Gatteschi Single-molecule Magnets , 2000 .

[21]  E. Bill,et al.  Exchange coupling in a bis(heterodinuclear) [CuIINiII]2 and a linear heterotrinuclear complex CoIIICuIINiII. Synthesis, structures and properties , 2000 .

[22]  E. Bill,et al.  On the rational synthesis and properties of exchange-coupled heterotrinuclear systems containing [MAMBMB] and [MAMBMC] cores , 2000 .

[23]  A. Scuiller,et al.  SOFT X-RAY MAGNETIC CIRCULAR DICHROISM IN PARAMAGNETIC SYSTEMS : ELEMENT-SPECIFIC MAGNETIZATION OF TWO HEPTANUCLEAR CRIII MII6 HIGH-SPIN MOLECULES , 1999 .

[24]  Masaaki Ohba,et al.  [Mn(en)]3[Cr(CN)6]2⋅4 H2O: ein Dimetall‐Ferrimagnet (Tc = 69 K) aus dreidimensional verknüpften, unvollständigen Kubaneinheiten , 1999 .

[25]  A. Caneschi,et al.  Single-Molecule Magnet Behavior of a Tetranuclear Iron(III) Complex. The Origin of Slow Magnetic Relaxation in Iron(III) Clusters , 1999 .

[26]  C. Trautwein,et al.  Encapsulation by a Chromium(III)-Containing Bicyclic Ligand Cage. Synthesis, Structures, and Physical Properties of Heterometal Complexes CrIIIMCrIII [M = (H+)2, Li(I), Mg(II), Cu(II), Ni(II), Ni(IV), Co(III), Fe(II), Fe(III), Mn(II)] , 1998 .

[27]  S. A. Kubow,et al.  Distortions from trigonal prismatic geometry for several structurally characterized clathrochelate complexes: significance of π-backbonding on clathrochelate coordination geometry , 1996 .

[28]  O. Kahn Magnetism of Heterobimetallics: Toward Molecular-Based Magnets , 1995 .

[29]  D. Hodgson,et al.  Heteronuclear trinuclear complex ions of the type [MII{Cr(A)4(OH)2}2]4+ , 1993 .

[30]  H. Wakita,et al.  The dithiooxalate-bridged complex [Cr(C2O2S2)3(NiL)3][ClO4]3(L = racemic 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane): synthesis, crystal structure and magnetism , 1993 .

[31]  E. Pedersen,et al.  Tetranuclear heterometallic complexes of the general types [M{(OH)2CrA4}3]5+ and [M{(OH)2CoA4}3]5+ , 1991 .

[32]  F. Lloret,et al.  Molecular topology exchange interaction: synthesis and magnetic properties of [Cu(II)3M(II)] (M = cadmium, nickel, manganese) tetranuclear species , 1990 .

[33]  W. Haase,et al.  A novel series of heterotrinuclear complexes with a tris(dimethylglyoximato)metal(II) anion as bridging ligand. Structure of the FeIIICuIIFeIII complex with S = 9/2 ground state , 1990 .

[34]  D. Luneau,et al.  Synthesis, structure, and magnetism of the trinuclear copper(II) complex [Cu(CuL)2][ClO4]2[H2L = 3,3′-(trimethylenedinitrilo)bis(2-butanone oxime)] , 1990 .

[35]  U. Thewalt,et al.  Heteronukleare Mehrkernkomplexe. Darstellung und Struktur von Komplexen mit den Kationen [MII{(OH)2CoIII(en)2}3]5+, M = Ni, Zn, Mg/Polynuclear Mixed-Metal Complexes. Preparation and Structures of Complexes with the Cations [MII{(OH)2CoIII(en)2}3]5+, M = Ni, Zn, Mg , 1989 .

[36]  O. Kahn,et al.  Ferromagnetic interactions between t2g3 and eg2 magnetic orbitals in a chromium(III)nickel(II)3 tetranuclear compound , 1989 .

[37]  K. Wieghardt,et al.  General route to .mu.-hydroxo-bis(.mu.-acetato)-bridged heterometal dinuclear complexes. Syntheses, magnetic and redox properties, electronic spectra, and molecular structures of the [Cr(III)-Co(II)] and [Cr(III)-Fe(II)] species , 1987 .

[38]  L. C. Andrews,et al.  The variable coordination chemistry of a potentially heptadentate ligand with a series of 3d transition metal ions. The chemistry and structures of [M(py3tren)]2+, where M(II) Mn, Fe, Co, Ni, Cu, and Zn and (py3tren) N{CH2CH2C(H)(C5H4N)}3 , 1987 .

[39]  R. Mukherjee,et al.  Trinucleation of arylazo oxime ensembles. 2. Linear iron(II)-nickel(II)-iron(II) and related systems , 1986 .

[40]  P. Corfield,et al.  Complexes of binucleating ligands with two different coordination environments. 4. Electrochemical properties and molecular structure of the heterobinuclear complex [5,5'-(1,2-ethanediyldinitrilo)bis(1-phenyl-1,3-hexanedionato)(4-)]nickelcopper, NiCu(BAA)2en , 1983 .

[41]  U. Hauser,et al.  Exchange interactions in tris[cis-di-.mu.-hydroxo-bis(ethylenediamine)chromium(III)]chromium(III) tris(dithionate)octahydrate , 1980 .

[42]  B. Sahoo,et al.  Transition metal cluster complexes—I , 1974 .

[43]  T. Berg,et al.  The chromium analogue of Werner's brown salt: isolation of tris[cis-di-µ-hydroxo-bis(ethylenediamine)chromium(III)]chromium(III) nitrate, [Cr{(OH)2Cr(en)2}3](NO3)6,aq , 1974 .

[44]  R. Wentworth Trigonal prismatic vs. octahedral stereochemistry in complexes derived from innocent ligands , 1972 .

[45]  G. Costa,et al.  Reactions of model molecules for vit. B12 with carbon monoxide , 1969 .

[46]  E. Sinn,et al.  Metal complexes as ligands—IV [1,2,3]: Bi- and Tri- nuclear complexes derived from metal complexes of tetradentate salicylaldimines , 1968 .