Magnetic Switching in Vapochromic Oxalato-Bridged 2D Copper(II)- Pyrazole Compounds for Biogenic Amine Sensing

A new two-dimensional (2D) coordination polymer of the formula {Cu(ox)(4-Hmpz)·1/3H2O}n (1) (ox = oxalate and 4-Hmpz = 4-methyl-1H-pyrazole) has been prepared, and its structure has been determined by single-crystal X-ray diffraction. It consists of corrugated oxalato-bridged copper(II) neutral layers featuring two alternating bridging modes of the oxalate group within each layer, the symmetric bis-bidentate (μ-κ2O1,O2:κ2O2′,O1′) and the asymmetric bis(bidentate/monodentate) (μ4-κO1:κ2O1,O2:κO2′:κ2O2′,O1′) coordination modes. The three crystallographically independent six-coordinate copper(II) ions that occur in 1 have tetragonally elongated surroundings with three oxygen atoms from two oxalate ligands, a methylpyrazole-nitrogen defining the equatorial plane, and two other oxalate-oxygen atoms occupying the axial positions. The monodentate 4-Hmpz ligands alternatively extrude above and below each oxalate-bridged copper(II) layer, and the water molecules of crystallization are located between the layers. Compound 1 exhibits a fast and selective adsorption of methylamine vapors to afford the adsorbate of formula {Cu(ox)(4-Hmpz)·3MeNH2·1/3H2O}n (2), which is accompanied by a concomitant color change from cyan to deep blue. Compound 2 transforms into {Cu(ox)(4-Hmpz)·MeNH2·1/3H2O}n (3) under vacuum for three hours. The cryomagnetic study of 1–3 revealed a unique switching from strong (1) to weak (2 and 3) antiferromagnetic interactions. The external control of the optical and magnetic properties along this series of compounds might make them suitable candidates for switching optical and magnetic devices for chemical sensing.

Study of risk factor of urinary calculi according to the association between stone composition with urine component

Urolithiasis is a common urinary disease with high recurrence. The risk factor for the recurrence of calculi is not very clear. The object of the present study was to evaluate the association between calculi composition and urine component and analyse the risk factor for the recurrence of urolithiasis. In this study, a total of 223 patients with calculi and healthy control were enrolled, and the components of the calculi and urina sanguinis collected before surgery were analysed. Of the 223 patients, 157 were males and 66 were females. According to the stone composition, the case group was subdivided into three groups. 129 patients had single calcium oxalate stones, 72 had calcium oxalate stones mixed with other stones and 22 had other type of stones excluding calcium oxalate stones. Urine biochemicals were analysed and the associations were found between the chemicals in each group. Multivariate logistic analysis demonstrated that reduced urinary magnesium and uric oxalic acid were independent risk factors when comparing all cases with normal controls. Only decreased urinary magnesium was found to be a risk factor comparing the single calcium oxalate group with normal control group. Low level of urinary magnesium and uric oxalic acid were found to be risk factors comparing the mixed calcium oxalate group with normal control group. No risk factor was found comparing the other stone group with normal control group. In conclusion, there were clear relationships between stone components and urine chemicals. Urine chemicals might be risk factors to predicate the occurrence of urolithiasis.

Fluorescent Recognition of Adenosine Triphosphate and Uric Acid by two Eu-Based Metal-Organic Frameworks

Two Eu-based MOF fluorescent sensors, Eu2(CHDA)2(C2O4)(H2O)4 (1) (CHDA = 1,4-cyclohexanedicarboxylic acid, C2O4 = oxalate group) and Eu2(PDA)3(H2O)3 (2) (p-Phenylenediacetic acid = PDA), were prepared for the rapid detection of uric...

Magnetic and Electrical Behaviors of the Homo- and Heterometallic 1D and 3D Coordination Polymers Based on the Partial Decomposition of the [Cr(C2O4)3]3− Building Block

One-dimensional (1D) oxalate-bridged homometallic {[Mn(bpy)(C2O4)]·1.5H2O}n (1) (bpy = 2,2’-bipyridine) and heterodimetallic {[CrCu3(bpy)3(CH3OH)(H2O)(C2O4)4][Cu(bpy)Cr(C2O4)3]·CH2Cl2·CH3OH·H2O}n (2) coordination polymers, as well as the three-dimensional (3D) heterotrimetallic {[CaCr2Cu2(phen)4(C2O4)6]·4CH3CN·2H2O}n (3) (1,10-phenanthroline) network, have been synthesized by a building block approach using a layering technique, and characterized by single-crystal X-ray diffraction, infrared (IR) and impedance spectroscopies and magnetization measurements. During the crystallization process partial decomposition of the tris(oxalato)chromate(III) happened and 1D polymers 1 and 2 were formed. The antiferromagnetic interactions between the manganese(II) ions were mediated by oxalate ligands in the chain [Mn(bpy)(C2O4)]n of 1, with intra-chain super-exchange interaction ? = (−3.134 ± 0.004) K; magnetic interaction between neighbouring chains is negligible making this system closer than other known Mn-chains to the ideal 1D Heisenberg antiferromagnet. Compound 2 comprises a 1D coordination anion [Cu(bpy)Cr(C2O4)3]nn− (Cr2–Cu4) with alternating [Cr(C2O4)3]3− and [Cu(bpy)]2+ units mutually bridged through the oxalate group. Another chain (Cr1–Cu3) is similar, but involves a homodinuclear unit [Cu(bpy)(H2O)(µ-C2O4)Cu(bpy)(CH3OH)]2+ (Cu1–Cu2) coordinated as a pendant group to a terminal oxalate oxygen. Magnetic measurements showed that the Cu1−Cu2 cationic unit is a strongly coupled antiferromagnetic dimer, independent from the other magnetic ions within ferromagnetic chains Cr1–Cu3 and Cr2–Cu4. A 3D polymer {[CaCr2Cu2(phen)4(C2O4)6]·4CH3CN·2H2O}n (3) comprising three different metal centers (Ca2+, Cr3+ and Cu2+) oxalate-bridged, contains Ca2+ atoms as nodes connected with four Cr3+ atoms through oxalate ligands. The network thus formed can be reduced to an underlying graph of diamondoid (dia) or (66) topology. Magnetization of 3 shows the ferromagnetic oxalate-bridged dimers [CuIICrIII], whose mutual interaction could possibly originate through the spin polarization of Ca2+ orbitals. Compounds 1 and 3 exhibit lower electrical conductivity at room temperature (RT) in comparison to compound 2.

Crystal structure of bis[4-(dimethylamino)pyridinium] aquabis(oxalato)oxidovanadate(IV) dihydrate

The title organic–inorganic hybrid salt, (C7H11N2)2[V(C2O4)2O(H2O)]·2H2O, shows a distorted octahedral coordination environment for the vanadium(IV) atom in the anion (point group symmetry 2), with four O atoms from two symmetry-related chelating oxalate dianions and two O atoms intransconfiguration from a coordinating water molecule and a terminal vanadyl O atom. In the crystal, (001) layers of cations and anions alternate along [001]. The anionic layers are built up by intermolecular O—H...O hydrogen bonds involving the coordinating and solvent water molecules. The cationic layers are linked to the anionic layersviaN—H...O hydrogen bonds between the pyridinium group and the non-coordinating O atoms of the oxalate group. The 4-(dimethylamino)pyridinium cations are also engaged in π–π stacking with their antiparallel neighbours [centroid-to-centroid distance = 3.686 (2) Å]. Considering all supramolecular features, a three-dimensional network structure is accomplished.

Magnetic Studies in Mixed-Metal Valency Molecule Magnets NBu4FeιιnMnιι1-n[Feιιι(OX)3](n=0.03, 0.10, 0.15, 0.97)

The mixed valency character and antiferromagnetic coupling in Molecule magnets Materials NBu4FeIInMnII1-n[FeIII(OX)3]（n=0.03、0.10、0.15、0.97） were investigated by magnetic measurements.The values of M increase and exhibit weak irreversibility in the field-cooled (FC) magnetization curves. There are a clear bifurcation phenomenon of the field-cooled (MFC) and Zero-field-cooled (MZFC) magnetization curves.In the Molecule magnets Materials NBu4FeII0.10 MnII0.90[FeIII(OX)3],the Ne´el temperature is 34 K.And the Ne´el temperature of NBu4FeII0.15MnII0.85 [FeIII(OX)3] is 28 K.In the sample NBu4FeII0.03 MnII0.97[FeIII(OX)3],,the bifurcation of the ZFC and FC plots below the Ne´el temperature of 30 K indicates irreversibility.The oxalate group has been shown to be an excellent bridging ligand in supporting the magnetic exchange interaction.