Structure and Magnetism of Cyano-Bridged Hetero-Binuclear Complexes RE(dpdo)2(H2O)3Fe(CN)6·4H2O (RE˭Gd, Y)

Abstract Two heterobinuclear cyano-bridged RE-Fe complexes RE(dpdo)2(H2O)3Fe(CN)6 ·4H2O (RE˭Gd,Y; dpdo=2,2′-Dipyridyl N.N′-Dioxide) were synthesized with identical structure. Gd-Fe complex crystallizes in triclinic crystal system, space group P-1 with a = 10.305(2), b = 12.475(1), c = 13.903(1)A, α = 85.34(1), β = 88.08(1), γ = 70.54(1)°, V = 1679.6(4) A3, Z = 2. In Gd-Fe binuclear unit, Gd3± is eight coordinated by one N atom from one CN− group, four O atoms from two bidentate dpdo molecules and three O atoms from water molecules, forming a square anti-prism. Gd and Fe are bridged via one CN− group from Fe(CN)6 3− ion with Gd-Fe separation 5.507(1)A. The nearest inter-molecular distances of Gd-Fe, Gd-Gd, Fe-Fe are 7.457(1), 7.984(1), and 8.409(1)A respectively. There are hydrogen bond intra- and inter-molecular connections. The intra-molecular coupling of Gd-Fe is weakly ferromagnetic, meanwhile the interactions between the binuclear units are weakly antiferromagnetic in character.

[1]  S. Decurtins,et al.  MOLECULAR CHROMIUM(III)-LANTHANIDE(III) COMPOUNDS (LN = LA, CE, PR, ND) WITH A POLYMERIC, LADDER-TYPE ARCHITECTURE : A STRUCTURAL AND MAGNETIC STUDY , 1998 .

[2]  S. Batten,et al.  Structure and Magnetism of a Bimetallic Pentanuclear Cluster [(Ni(bpm)2)3(Fe(CN)6)2]·7H2O (bpm = Bis(1-pyrazolyl)methane)). The Role of the Hydrogen-Bonded 7H2O “Cluster” in Long-Range Magnetic Ordering , 1997 .

[3]  F. Dahan,et al.  A General Route to Strictly Dinuclear Cu(II)/Ln(III) Complexes. Structural Determination and Magnetic Behavior of Two Cu(II)/Gd(III) Complexes. , 1997, Inorganic chemistry.

[4]  O. Kahn,et al.  Design and Magnetic Properties of a Magnetically Isolated GdIIICuII Pair. Crystal Structures of [Gd(hfa)3Cu(salen)], [Y(hfa)3Cu(salen)], [Gd(hfa)3Cu(salen)(Meim)], and [La(hfa)3(H2O)Cu(salen)] [hfa = Hexafluoroacetylacetonato, salen = N,N‘-Ethylenebis(salicylideneaminato), Meim = 1-Methylimidazole] , 1997 .

[5]  A. Caneschi,et al.  Crystal and molecular structure of and magnetic coupling in two complexes containing gadolinium(III) and copper(II) ions , 1985 .

[6]  F. Hulliger,et al.  Rare-earth ferricyanides and chromicyanides LnT(CN)6·nH2O , 1976 .

[7]  C. Floriani,et al.  Assembling Bi-, Tri- and Pentanuclear Complexes into Extended Structures Using a Desolvation Reaction: Synthesis, Structure, and Magnetic Properties of Manganese(III)-Schiff-Base-Hexacyanoferrate Polymeric Compounds and Their Derived Extended Structures , 1998 .

[8]  Song Gao,et al.  Edta-linked 4f-3d heterometallic two dimensional sheet in Ln2M3(edta)3(H2O)11·12H2O (LnNd, Gd; MMn, Co) , 1998 .

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

[10]  O. Kahn Magnetism of the heteropolymetallic systems , 1987 .