CoGd Cage as Magnetic Refrigerant and CoDy Cage Showing Slow Relaxation of Magnetisation.

Two structurally dissimilar 3d-4f cages having the formulae [(Co)Gd(μ-OH)(CO) (OCBu)(teaH)]·5HO () and [(Co)Dy(μ-OH)(OCBu)(teaH)]·(NO)·HO () have been isolated under similar reaction conditions and stoichiometry of the reactants. The most important factor for structural diversity seems to be the incorporation of one μ-carbonate anion in and not in . Co atoms are in a +3 oxidation state in both complexes, as shown by the Bond Valence Sum (BVS) calculations and bond lengths, and as further supported by magnetic measurements.

Layered metal(IV) phosphonate materials: Solid-state H, C, P NMR spectra and NMR relaxation.

Multinuclear solid-state NMR and powder X-ray diffraction data collected for phosphonate materials Zr(O PC H PO ) · 3.6H O and Sn(O PC H PO ) (O POH)  · 3.09H O have resulted in the layered structure, where the phosphonic acids cross-link the layers.

Achieving Amphibious Superprotonic Conductivity in a Cu Metal-Organic Framework by Strategic Pyrazinium Salt Impregnation.

Treatment of a pyrazine (pz)-impregnated Cu metal-organic framework (MOF) ([1⊃pz]) with HCl vapor renders an interstitial pyrazinium chloride salt-hybridized MOF ([1⊃pz⋅6 HCl]) that exhibits proton conductivity over 10  S cm both in anhydrous and under humid conditions. Framework [1⊃pz⋅6 HCl] features the highest anhydrous proton conductivity among the lesser-known examples of MOF-based materials exhibiting proton conductivity under both anhydrous and humid conditions. Moreover, [1⊃pz] and corresponding pyrazinium sulfate- and pyrazinium phosphate-hybridized MOFs also exhibit superprotonic conductivity over 10  S cm under humid conditions.

To Evaluate the Effectiveness of TBTS - A Novel Device to do Self-Stretching of Gastroc-Soleus Muscle in Patients with Equinus Deformity.

Introduction: Various methods have been used for management of equinus deformity. However, stretching gastroc-soleus muscle and achilles tendon is a difficult task. It is labour intensive, which makes the provision of treatment difficult for many patients.

Modulating Magnetic Refrigeration through Structural Variation in Co-Gd Clusters.

Three heterometallic aggregates, [(Co)(Gd)(BuPO)(OCBu)(HOCBu)(NO)]·NEt (1), [(Co)(Co)(Gd)(μ-OH)(BuPO)(OCBu)(deaH)(HO)] (2), and (Co)(Gd)(μ-OH)(μ-OH)(BuPO)(OCBu)(HOCBu)(deaH)]·MeOH (3), were successfully isolated in reactions of [Co(μ-OH)(OCBu)]·(HOCBu), Gd(NO)·6HO, Bu-POH, and diethanolamine (deaH) by varying the stoichiometry of the reactants and/or changing the solvent. The structures of the final products were profoundly affected by these minor changes in stoichiometry or a change in solvent. The metal-oxo core of these complexes displays a hemicubane or a defective dicubane-like view.

Modification and intercalation of layered zirconium phosphates: a solid-state NMR monitoring.

Several layered zirconium phosphates treated with Zr(IV) ions, modified by monomethoxy-polyethyleneglycol-monophosphate and intercalated with doxorubicin hydrochloride have been studied by solid-state MAS NMR techniques. The organic components of the phosphates have been characterized by the C{ H} CP MAS NMR spectra compared with those of initial compounds. The multinuclear NMR monitoring has provided to establish structure and covalent attachment of organic/inorganic moieties to the surface and interlayer spaces of the phosphates.

Heterometallic Co(III)-Gd(III) Clusters as Magnetic Refrigerants.

Two heterometallic Co(III)-Gd(III) nanomagnets (Co2Gd6 and Co2Gd9) with defective dicubane-like cores were isolated from the same set of reactants by varying the reaction conditions. These are the first examples of cobalt(III)-gadolinium(III) phosphonate compounds and a rare class of compounds with large 4f ratio among the reported 3d-4f complexes. Magnetic studies reveal large magnetic entropy changes for both complexes (-ΔSm = 27.

Phosphonate Based High Nuclearity Magnetic Cages.

Transition metal based high nuclearity molecular magnetic cages are a very important class of compounds owing to their potential applications in fabricating new generation molecular magnets such as single molecular magnets, magnetic refrigerants, etc. Most of the reported polynuclear cages contain carboxylates or alkoxides as ligands. However, the binding ability of phosphonates with transition metal ions is stronger than the carboxylates or alkoxides.

Modulating the magnetic properties by structural modification in a family of Co-Ln (Ln = Gd, Dy) molecular aggregates.

Two types of heterometallic aggregates of the general formula [(Co(II))3(Co(III))2Ln3(μ3-OH)5(O2C(t)Bu)12(L)2]·2H2O (Ln = Gd(III) (), Dy(III) ()) and [(Co(III))3Ln3(μ3-OH)4(O2C(t)Bu)6(L)3](NO3)2·2CH3CN·2H2O (Ln = Gd(III) (), Dy(III) ()) were successfully isolated in reactions with [Co2(μ-OH2)(O2C(t)Bu)4]·(HO2C(t)Bu)4, Ln(NO3)3 and n-N-butyldiethanolamine (H2L) under ambient conditions by a change in the stoichiometry of the reactants from 1 : 1 : 1 to 1 : 1 : 2 in order. Bond Valence Sum (BVS) calculations and bond lengths indicate the presence of mixed valent Co (Co(II), Co(III)) centres in compounds and and only Co(III) centres in and as required for the charge balances and supported by the magnetic measurements. Isostructural crab shaped complexes and feature distorted cubane cores that edge share to each other whereas the metallic core of or displays hemicubane like arrangement of metal centres and oxygen atoms.

Synthesis, crystal structure and study of magnetocaloric effect and single molecular magnetic behaviour in discrete lanthanide complexes.

The synthesis, crystal structure and magnetic properties of four polynuclear lanthanide coordination complexes having molecular formulae, [Gd3(2)(1)L(H2O)8(Cl)](Cl)4·10H2O (1), [Dy3L(2)(1)(H2O)9](Cl)5·6H2O (2) [Gd6L(2)(2)(HCO2)4(μ3-OH)4(DMF)6(H2O)2](Cl)2·4H2O (3) and [Dy6L(2)(2)(HCO2)4(μ3-OH)4(DMF)6(H2O)2](Cl)2·4H2O (4) (where H2L(1) = bis[(2-pyridyl)methylene]pyridine-2,6-dicarbohydrazide and H4L(2) = bis[2-hydroxy-benzylidene]pyridine-2,6-dicarbohydrazide) are reported. Structural investigation by X-ray crystallography reveals similar structural features for complexes 1 and 2 and they exhibit butterfly like shapes of the molecules. Non-covalent interactions between the molecules create double helical arrangements for both molecules.

High nuclearity (octa-, dodeca-, and pentadecanuclear) metal (M = Co(II), Ni(II)) phosphonate cages: synthesis, structure, and magnetic behavior.

The synthesis, structural characterization, and magnetic property studies of five new transition metal (M = Co, Ni) phosphonate-based cages are reported. Three substituted phenyl and benzyl phosphonate ligands [RPO3H2; R1 = p-tert-butylbenzyl, R2 = p-tert-butylphenyl, R3 = 3-chlorobenzyl] were synthesized and employed to seek out high-nuclearity cages. Complexes 1-3 are quasi-isostructural and feature a dodecanuclear metal-oxo core having the general molecular formula of [M12(μ3-OH)4 (O3PR)4(O2C(t)Bu)6 (HO2C(t)Bu)6(HCO3)6] {M = Co, Ni and R = R1 for 1 (Co12), R2 for 2, 3 (Co12, Ni12)}.

An unprecedented octadecanuclear copper(II) pyrazolate-phosphonate nanocage: synthetic, structural, magnetic, and mechanistic study.

A novel octadecanuclear copper pyrazolate-phosphonate nanocage with a bowl-shaped arrangement of the copper(II) centers in the asymmetric unit is reported. Characterization of intermediates in both solid and solution states aids to propose the mechanism of such a giant aggregation. Magnetic studies affirm the presence of antiferromagnetic interactions between the adjacent copper(II) centers.

Serendipitous assemblies of two large phosphonate cages: a Co15 distorted molecular cube and a Co12 butterfly type core structure.

This report describes the synthesis, characterization, and magnetic properties of two novel phosphonate-based Co(II) cages. Structural investigation reveals some interesting geometrical features in the molecular core that may provide new models in single molecular magnetic materials.

Intramolecular direct dehydrohalide coupling promoted by KO(t)Bu: total synthesis of Amaryllidaceae alkaloids anhydrolycorinone and oxoassoanine.

A transition-metal-free intramolecular dehydrohalide coupling via intramolecular homolytic aromatic substitution (HAS) with aryl radicals has been developed in the presence of potassium tert-butoxide and an organic molecule as the catalyst. The methodology has been applied to a concise synthesis of Amaryllidaceae alkaloids viz. oxoassoanine (1b), anhydrolycorinone (1d), and other related structures.