Synthesis, structure, and magnetism of heterobimetallic trinuclear complexes {[L2Co2Ln][X]} [Ln = Eu, X = Cl; Ln = Tb, Dy, Ho, X = NO3; LH3 = (S)P[N(Me)N=CH-C6H3-2-OH-3-OMe]3]: A 3d-4f family of single-molecule magnets.

Department of Chemistry, Indian Institute of Technology-Kanpur, Kanpur-208016, India.
Inorganic Chemistry (Impact Factor: 4.59). 02/2009; 48(3):1148-57. DOI: 10.1021/ic801905p
Source: PubMed

ABSTRACT Sequential reaction of LH3 (LH3 = (S)P[N(Me)N=CH-C6H3-2-OH-3-OMe]3) with Co(OAc)2 x 4 H2O followed by reaction with lanthanide salts afforded trinuclear heterobimetalllic compounds {[L2Co2Ln][X]} [Ln = Eu (1), X = Cl; Ln = Tb (2), Dy (3), Ho (4), X = NO3] in excellent yields. These compounds retain their integrity in solution as determined by electrospray ionization mass spectrometry studies. The molecular structures of 1-4 were confirmed by a single-crystal X-ray structural study and reveal that these are isostructural. In all of the compounds, the three metal ions are arranged in a perfectly linear manner and are held together by two trianionic ligands, L3-. The two terminal Co(II) ions contain a facial coordination environment (3N, 3O) comprising three imino nitrogen atoms and three phenolate oxygen atoms. The coordination geometry about the cobalt atom is severely distorted. An all-oxygen coordination environment (12O) is present around the central lanthanide ion, which is present in a distorted icosahedral geometry. The coordination sphere around the lanthanide ion is achieved by utilizing three phenolate oxygen atoms and three methoxy oxygen atoms of each ligand. In all of these trinuclear complexes (1-4), the Co-Ln distances are around 3.3 A, while the Co-Co distances range from 6.54 to 6.60 A. The screw-type coordination mode imposed by the ligand induces chirality in the molecular structure, although all of the complexes crystallize as racemates. Magnetic properties of 1-4 have been studied in detail using dc and ac susceptibility measurements. Dynamic measurements reveal that 2-4 display a single-molecule magnet behavior, while the Co2Eu (1) analogue does not show any out-of-phase ac susceptibility.

  • Source
    [Show abstract] [Hide abstract]
    ABSTRACT: The reaction of 8-quinolinol-2-carboaldoxime (LH2) with Ni(II) and Ln(III) salts afforded the heterometallic decanuclear compounds [Ni8Dy2(μ3-OH)2(L)8(LH)2(H2O)6](ClO4)2·16H2O (), [Ni8Gd2(μ3-OH)2(L)8(LH)2(H2O)4(MeOH)2](NO3)2·12H2O (), [Ni8Ho2(μ3-OH)2(L)8(LH)2(H2O)4(MeOH)2](ClO4)2·2MeOH·12H2O () and [Ni8Tb2 (μ3-OH)2(L)8(LH)2(MeOH)4(OMe)2]·2CH2Cl2·8H2O (). While compounds are dicationic, compound is neutral. These compounds possess an S-shaped architecture and comprise a long chain of metal ions bound to each other. In all the complexes, the eight Ni(II) and two Ln(III) ions of the multimetallic ensemble are hold together by two μ3-OH, eight dianionic (L(2-)) and two monoanionic oxime ligands (LH(-)) whereas compound has two μ3-OH, eight dianionic (L(2-)), two monoanionic oxime ligands (LH(-)) and two terminal methoxy (MeO(-)) ligands. The central portion of the S-shaped molecular wire is made up of an octanuclear Ni(II) ensemble which has at its two ends the Ln(III) caps. Magnetic studies on reveal that the magnetic interactions between neighboring metal ions are negligible at room temperature. On the other hand, at lower temperatures in all the compounds anti-ferromagnetic interactions seem to be dominated. Analysis of the magnetic data for the Gd(III) derivative indicates Ni(II)-Ni(II) anti-ferromagnetic interactions and Gd(III)-Ni(II) ferromagnetic interactions at low temperatures. A theoretical density functional study on the magnetic behavior of the Gd(III) derivative suggests that while the weak ferromagnetic interaction between Gd(III) and Ni(II) is in line with the expectation of the magnetic interactions between orthogonal d and f orbitals, antiferromagnetic Ni(II)-Ni(II) interactions are related to the wide Ni-O-Ni angles (∼102°) and quasi-planar conformation of the Ni2O2 core.
    Dalton transactions (Cambridge, England : 2003). 05/2014;
  • Source
    [Show abstract] [Hide abstract]
    ABSTRACT: The synthesis and characterization of four dinuclear 3d-4f complexes [M(II)Ln(III)(L)(DBM)3] (ZnDy = , CoY = , CoDy = ·3.5CH3CN, CoGd = ·3.5CH3CN) are reported (H2L = N,N'-dimethyl-N,N'-(2-hydroxy-3-methoxy-5-methyl-benzyl)ethylenediamine, DBM(-) = anion of 1,3-diphenyl-propane-1,3-dione). In each of the four complexes, the M(II) ion occupies the internal N2O2 site whereas the Ln(III) ion occupies the external O4 site. There are diphenoxo bridges between the M(II) and Ln(III) ions in these complexes. The remaining coordination sites are occupied by three DBM(-) anions. Direct current (dc) magnetic susceptibility measurements indicate the presence of intramolecular ferromagnetic interactions in complexes and . The magnetic coupling constant, JCoGd, of complex is estimated to be 0.26 cm(-1) (H = -2JCoGdSCoSGd). Alternating current (ac) magnetic susceptibility studies reveal that complexes and show field-induced single molecule magnet behavior, with ΔE values of 36.5 K and 8.56 K, respectively. Complex shows frequency dependent out-of-phase signals, indicating the presence of a slow relaxation of the magnetization, whereas complex does not display slow magnetization relaxation.
    Dalton transactions (Cambridge, England : 2003). 06/2014; 43:11309.
  • [Show abstract] [Hide abstract]
    ABSTRACT: The use of LH3 (2-(β-naphthalideneamino)-2-hydroxymethyl-1-propanol) and aibH (2-amino-isobutyric acid) in 4f chemistry has led to the isolation of eight new isostructural lanthanide complexes. More specifically, the reaction of the corresponding lanthanide nitrate salt with LH3 and aibH in MeOH, under solvothermal conditions in the presence of NEt3, led to the isolation and characterization of seven complexes with the general formulae [Ln(III)7(OH)2(L')9(aib)]·4MeOH (Ln = Gd, ·4MeOH; Tb, ·4MeOH; Dy, ·4MeOH; Ho, ·4MeOH; Er, ·4MeOH; Tm, ·4MeOH; Yb, ·4MeOH L' = the dianion of the Schiff base between naphthalene aldehyde and 2-amino-isobutyric acid). Furthermore, the isostructural Y(III) analogue, cluster [Y(III)7(OH)2(L')9(aib)]·4MeOH (·4MeOH), was synthesized in a similar manner to . The structure of all eight clusters describes a distorted [M(III)6] octahedron which encapsulates a seventh M(III) ion in an off-centre fashion. Dc magnetic susceptibility studies in the 5-300 K range for complexes reveal the presence of dominant antiferromagnetic exchange interactions within the metallic clusters as evidenced by the negative Weiss constant, θ, while ac magnetic susceptibility measurements show temperature and frequency dependent out-of-phase signals for the [Dy(III)7] analogue (·4MeOH), suggesting potential single molecule magnetism character. Furthermore, for complex , simulation of its dc magnetic susceptibility data yielded very weak antiferromagnetic interactions within the metallic centres. Solid-state emission studies for all clusters display ligand-based emission, while extended 1D and 2D NMR studies for ·4MeOH reveal that the species retain their structural integrity in solution. In addition, TGA measurements for , and revealed excellent thermal stability up to 340 °C for the clusters.
    Dalton Transactions 05/2014; · 3.81 Impact Factor