Two-dimensional 3d-4f heterometallic coordination polymers: syntheses, crystal structures, and magnetic properties of six new Co(II)-Ln(III) compounds.

Six new heterometallic cobalt(II)-lanthanide(III) complexes of formulas [Ln(bta)(H2O)2]2[Co(H2O)6]·10H2O [Ln = Nd(III) (1) and Eu(III) (2)] and [Ln2Co(bta)2(H2O)8]n·6nH2O [Ln = Eu(III) (3), Sm(III) (4), Gd(III) (5), and Tb(III) (6)] (H4bta = 1,2,4,5-benzenetretracaboxylic acid) have been synthesized and characterized via single-crystal X-ray diffraction. 1 and 2 are isostructural compounds with a structure composed of anionic layers of [Ln(bta)(H2O)2]n(n-) sandwiching mononuclear [Co(H2O)6](2+) cations plus crystallization water molecules, which are interlinked by electrostatic forces and hydrogen bonds, leading to a supramolecular three-dimensional network. 3-6 are also isostructural compounds, and their structure consists of neutral layers of formula [Ln2Co(bta)2(H2O)8]n and crystallization water molecules, which are connected through hydrogen bonds to afford a supramolecular three-dimensional network.

Synthesis, crystal structure, and magnetic characterization of the three-dimensional compound [Co2(cbut)(H2O)3]n (H4cbut = 1,2,3,4-cyclobutanetetracarboxylic acid).

A novel cobalt(II) complex of formula [Co2(cbut)(H2O)3]n (1) (H4cbut = 1,2,3,4-cyclobutanetetracarboxylic acid) has been synthesized under hydrothermal conditions and its crystal structure has been determined by means of synchrotron radiation and neutron powder diffraction. The crystal structure of 1 consists of layers of cobalt(II) ions extending in the bc-plane which are pillared along the crystallographic a-axis through the skeleton of the cbut(4-) ligand. Three crystallographically independent cobalt(II) ions [Co(1), Co(2), and Co(3)] occur in 1.

Three new europium(III) methanetriacetate metal-organic frameworks: the influence of synthesis on the product topology.

Three new metal-organic framework structures containing Eu(III) and the little explored methanetriacetate (C7H7O6(3-), mta(3-)) ligand have been synthesized. Gel synthesis yields a two-dimensional framework with the formula [Eu(mta)(H2O)3]n·2nH2O, (I), while two polymorphs of the three-dimensional framework material [Eu(mta)(H2O)]n·nH2O, (II) and (III), are obtained through hydrothermal synthesis at either 423 or 443 K. Compounds (I) and (II) are isomorphous with previously reported Gd(III) compounds, but compound (III) constitutes a new phase.

Neutron diffraction studies of the molecular compound [Co2(bta)]n (H4bta =1,2,4,5-benzenetetracarboxylic acid): in the quest of canted ferromagnetism.

The exchange mechanism and magnetic structure of the organic-inorganic layered molecule-based magnet [Co2(bta)]n (1) (H4bta =1,2,4,5-benzenetetracarboxylic acid) have been investigated through variable-temperature magnetic susceptibility measurements and supported with a series of neutron diffraction experiments. Cryomagnetic studies have shown an antiferromagnetic ordering at a transition temperature of 16 K that is followed by the appearance of a weak ferromagnetism below 11 K. The weak antiferromagnetic interlayer interaction plays an important role in this system in spite of the long interlayer separation.