Search results for "Ordination"
showing 10 items of 1367 documents
Divalent metal phosphonates – new aspects for syntheses, in situ characterization and structure solution
2016
Abstract Divalent metal phosphonates are promising hybrid materials with a broad field of application. The rich coordination chemistry of the phosphonate linkers enables the formation of structures with different dimensionalities ranging from isolated complexes and layered structures to porous frameworks incorporating various functionalities through the choice of the building blocks. In brief, metal phosphonates offer an interesting opportunity for the design of multifunctional materials. Here, we provide a short review on the class of divalent metal phosphonates discussing their syntheses, structures, and applications. We present the advantages of the recently introduced mechanochemical pa…
Preface for the Forum on Molecular Magnetism: The Role of Inorganic Chemistry
2009
Molecular magnetism is a rapidly expanding field of research whose central theme is the design and study of magnetic molecules and materials with tunable properties. In the early stages of the field, which began to take shape in the 1980s, much of the effort was directed at the pursuit of molecule-based magnetic solids that order at high temperatures. These materials are basically of two types: those based on tetracyanoethylene (TCNE) and those based on cyanide. As the field rapidly evolved over the past two decades, exciting new challenges appeared on the horizon, including the use of building block approaches for the preparation of complex multifunctional magnetic materials, the fabricati…
Oxalate‐Based 3D Chiral Magnets: The Series [Z II (bpy) 3 ][ClO 4 ][M II Fe III (ox) 3 ] (Z II = Fe, Ru; M II = Mn, Fe; bpy = 2,2'‐Bipyridine; ox = O…
2005
The synthesis, structure, and physical properties of the oxalate-based molecular magnets with the formula [ZII(bpy)3][ClO4][MIIFeIII(ox)3] (ZII = Fe, Ru; MII = Mn, Fe; bpy = 2,2'-bipyridine; ox = oxalate dianion) are presented here. All compounds are isostructural and crystallize in the chiral cubic space group P4132, and contain three-dimensional dimetallic networks formed by alternating MII and MIII ions that are connected by oxalate anions. These compounds exhibit strong antiferromagnetic interactions that give rise to magnetic ordering as ferrimagnets or weak ferromagnets, with critical temperatures of up to 20 K, which is twice as high as those found for the isostructural magnets based…
2D Bimetallic Oxalate‐Based Ferromagnets with Inserted [Fe(4‐Br‐sal 2 ‐trien)] + and [Fe(3‐R‐sal 2 ‐trien)] + (R = Br, Cl and CH 3 O) Fe III Spin‐Cro…
2012
The syntheses, structures and magnetic properties of the compounds of formula [FeIII(4-Br-sal2-trien)][MnIICrIII(ox)3]0.67Cl0.33·CH3OH_solvate (1), [FeIII(3-Br-sal2-trien)][MnIICrIII(ox)3]·(CH3CN)2 (2), [FeIII(3-Cl-sal2-trien)][MnIICrIII(ox)3]·(CH3OH)2·(CH3CN)2 (3) and [FeIII(3-CH3O-sal2-trien)][MnIICrIII(ox)3]·(CH3OH)·(H2O)1.5·(CH2Cl2)0.5 (4) are reported. The four structures present a 2D honeycomb anionic layer formed by MnII and CrIII ions linked through oxalate ligands and a cationic layer of the FeIII complexes intercalated between the 2D oxalate network. The main differences compared with previous 2D oxalate-based structures are the presence of double layers of cations in compounds 1,…
Cyclic voltammetric analysis of pH-dependent complex formation equilibria in anion coordination chemistry
1995
A procedure to analyze pH-dependent complex formation equilibria from cyclic voltammetry is described. Application to adduct formation equilibria between [Fe(CN)(6)](4-) and [Fe(CN)(6)](3-) with different polyammonium receptors is discussed. Extension to the interaction of substrates such as ATP, NAD(+), NADP(+), and carboxylate ions with these receptors by means of competitive interaction with hexacyanoferrate(II) ion is presented.
Protonation, coordination chemistry, cyanometallate "supercomplex" formation and fluorescence chemosensing properties of a bis(2,2'-bipyridino)cyclop…
2013
A new polyazamacrocycle (L) containing two 2,2'-bipyridino (bpy) units, where the heteroaromatic nitrogen atoms point outwards from the macrocyclic cavity, was synthesized and characterized by elemental analysis, ESI-MS, (1)H and (13)C NMR, FTIR and TGA. Five protonation constants involving aliphatic nitrogens with log K in the range 9.39-3.07 were determined by potentiometry and NMR and a sixth protonation (log K = 2.2) involving a bipyridine moiety could be detected by UV-Vis and NMR titrations. The interaction of L with the cyanometallate anions [Pt(CN)4](2-) and [Co(CN)6](3-) was studied by potentiometry yielding respectively log K values in the ranges 4.0-6.4 and 5.2-10.5, covering pro…
Spin crossover FeII complexes as templates for bimetallic oxalate-based 3D magnets
2007
Abstract We present the synthesis and structural characterization of the salt [Fe(bpp)2][MnCr(ox)3]2 · bpp · CH3OH. It crystallizes in the monoclinic space group. This material contains an anionic [MnCr(ox)3]− 3D 10-gon ferromagnetic network, that orders below 3.0 K. The channels created by this architecture are filled by the spin crossover cations [Fe(bpp)2]2+ (bpp = 2,6(bispyrazol-3-yl)pyridine), free ligand and solvent molecules. No spin transition has been observed at ambient pressure.
Experimental and theoretical investigations of the redox behavior of the heterodichalcogenido ligands [(EP(i)Pr2)(TeP(i)Pr2)N](-) (E = S, Se): cyclic…
2008
The two-electron oxidation of the lithium salts of the heterodichalcogenidoimidodiphosphinate anions [(EP (i)Pr 2)(TeP (i)Pr 2)N] (-) ( 1a, E = S; 1b, E = Se) with iodine yields cyclic cations [(EP (i)Pr 2)(TeP (i)Pr 2)N] (+) as their iodide salts [(SP (i)Pr 2)(TeP (i)Pr 2)N]I ( 2a) and [(SeP (i)Pr 2)(TeP (i)Pr 2)N]I ( 2b). The five-membered rings in 2a and 2b both display an elongated E-Te bond as a consequence of an interaction between tellurium and the iodide anion. One-electron reduction of 2a and 2b with cobaltocene produces the neutral dimers (EP (i)Pr 2NP (i)Pr 2Te-) 2 ( 3a, E = S; 3b, E = Se), which are connected exclusively through a Te-Te bond. Two-electron reduction of 2a and 2b …
A novel mixed valent Cu(II)-Cu(I) 2D framework made of a hydrazone and μ-SCN bridged metallacyclic loops cross-linked by μ3-SCN chains.
2012
A mixed valent copper complex [Cu(II)Cu(I)(L)(μ-SCN)(μ(3)-SCN)](n) (LH = N'-((pyridin-2-yl)methylene)acetohydrazide) has been synthesized and characterized. It is a unique example of a 2D mixed valent Cu(II)-Cu(I) interlinked molecular assembly with a very unusual bridging property of the hydrazone ligand. An extraordinary in situ partial Cu(II)→ Cu(I) reduction is observed in this system at room temperature.