A 3D Silverton-Type Polyoxomolybdate Based on {PrMo12O42}: Synthesis, Structure, Photoluminescence and Magnetic Properties

A three-dimensional (3D) Silverton-type polyoxomolybdate (POMo) with the formula of NH4{Mn4[PrMo12O42]}·18H2O (1) was successfully isolated and well characterized by single crystal X-ray diffraction, X-ray powder diffraction pattern, infrared spectrum, thermogravimetric and elemental analyses. The inorganic building block {PrMo12O42} has formed 3D frameworks via the {MnO6} linker. The excitation of compound 1 in solid state at 375 nm displays red emission. Moreover, variable temperature magnetic susceptibility measurements indicate that the magnetic behavior in compound 1 is dominated by antiferromagnetic interactions.

Supramolecular Assemblies of Trinuclear Copper(II)-Pyrazolato Units: A Structural, Magnetic and EPR Study

Two anionic complexes, {[Cu3(µ3-OH)(µ-4-Ph-pz)3Cl3]2[Cu(4-Ph-pzH)4](µ-Cl)2}2− (1) and [Cu3(µ3-OH)(µ-pz)3(µ1,1-N3)2(N3)]− (2), crystallize as one-dimensional polymers, held together by weak Cu-(µ-Cl) and Cu-(µ-N3) interactions, respectively. Variable temperature magnetic susceptibility analyses determined the dominant antiferromagnetic intra-Cu3 exchange parameters in the solid state for both complexes, whereas the weak ferromagnetic inter-Cu3 interactions manifested also in the solid state EPR spectra, are absent in the corresponding frozen solution spectra. DFT calculations were employed to support the results of the magnetic susceptibility analyses.

A new binuclear NiII complex with tetrafluorophthalate and 2,2′-bipyridine ligands: synthesis, crystal structure and magnetic properties

A new NiII compound, [Ni2(tfpa)2(bipy)2(H2O)4] (1) with tetrafluorophthalate (tfpa2−) and 2,2′-bipyridine (abbreviated as bipy) ligands, has been synthesized and structurally characterized. The single-crystal X-ray diffraction analysis reveals that the tfpa2− anions act as bis-monodentate linkers connecting NiII centers to form the dinuclear structure of 1. The dimeric units are stabilized by intramolecular π–π stacking and are further connected into a layer through O–HLO hydrogen bonding. Variable-temperature magnetic susceptibility data in the 10–200 K temperature range indicate weak ferromagnetic coupling between the two NiII ions.

Synthesis, Crystal Structures and Magnetic Properties of Mixed-Valent Tetranuclear Complexes with Y-Shaped MnII2MnIII2 Core

Tetranuclear MnII2MnIII2 complexes with 1,3-bis(5-bromo-3-metoxysalicylidenaminomethyl)-2-propanol (H3bmsap) and 1,3-bis(5-chloro-3-methoxysalicylidenaminomethyl)-2-propanol (H3cmsap), [Mn4(bmsap)2(CH3CO2)3(CH3O)] (3) and [Mn4(cmsap)2(CH3CO2)3(CH3O)] (4), were synthesized and characterized by elemental analysis, infrared and diffused reflectance spectra and variable-temperature magnetic susceptibility measurements in the 2–300 K range. The crystal structures of 3 and 4 revealed a Y-shaped tetranuclear manganese cluster formed by the two Schiff-base ligands, three kinds of acetato ligands (bidentate, syn–anti-bridging, and syn–syn-bridging), and µ-methoxido ligand. The magnetic data showed the magnetic interactions among the four manganese atoms are antiferromagnetic as a whole within the tetranuclear cluster.

Synthesis, Characterization and Magnetic Studies of a Tetranuclear Manganese(II/IV) Compound Incorporating an Amino-Alcohol Derived Schiff Base

A new tetranuclear mixed-valence manganese(II/IV) compound [MnIIMnIV3(μ-Cl)3(µ3-O)(L)3] (1) (where H3L = (3E)-3-((Z)-4-hydroxy-4-phenylbut-3-en-2-ylideneamino)propane-1,2-diol) has been synthesized and characterized by different physicochemical methods. Single crystal X-ray diffraction analysis reveals that 1 is a tetrahedral cluster consisting of a Mn4Cl3O4 core in which the only Mn(II) ion is joined through three μ2-O bridges to an equilateral triangle of Mn(IV) ions, which are connected by a μ3-O and three μ2-Cl bridges. The redox behavior of 1 was studied by cyclic voltammetry. Variable temperature magnetic susceptibility measurements of 1 revealed predominant antiferromagnetic coupling inside the Mn4Cl3O4 cluster.

Synthesis, structure and magnetic properties of a binuclear copper(II) complex constructed by a new coordination mode of the tetrachlorophthalate ligand

A binuclear complex [Cu2(tcpa)2(bipy)2(H2O)3] (1) (H4tcpa = tetrachlorophthalic acid, bipy = 2,2′-bipyridine) has been synthesized and structurally characterized. Two independent CuII centers Cu1 and Cu2 are both five-coordinated in distorted square pyramids. The tetrachlorophthalate (tcpa2–) anions show a new coordination mode: one is monodentate at Cu1, and the other displays a bridging μ2-O,O″ fashion linking Cu1 and Cu2, thus forming the binuclear structure of 1. Variable-temperature magnetic susceptibility data show weak antiferromagnetic coupling between the two CuII ions.

Preparation, electrochemical behavior, and variable-temperature magnetic properties of Co(3,5-DBSQ)2 complexes of imidazole- or pyrazole-substituted ligands

Herein we describe the preparation of four new Co(3,5-DBSQ)2 containing known 2-(2-pyridyl)benzimidazole 1, 2,2′-bisbenzimidazole 2, or 2,2-(1H-pyrazole-3,5-diyl)dipyridine 3. We investigate the electronic and variable-temperature magnetic susceptibility properties of these complexes. Complexes containing 2 and 3 are bimetallic and variable-temperature magnetic susceptibility data suggest observation of a stable intermediate (high-spin and low-spin) state for the bimetallic complex with 3, which does undergo valence tautomerism. Complexes 4–6 containing imidazole-based ligands 1 and 2 feature high-spin ground states and no valence tautomerism is observed in these materials. This experimental finding is corroborated with density functional theory calculations, which support the existence of a stable high-spin ground state in these complexes.

Structure and magnetic properties of an unusual homoleptic iron(iii) thiocyanate dimer

We describe the structural and variable temperature magnetic susceptibility properties of an unusual homoleptic bimetallic iron(iii) thiocyanate tetraanion.

Unusual potassium-oxalate coordination in the two-dimensional trimetallic [CoCl(NH3)5][KCr(C2O4)3]·0.5H2O complex

A new heterometallic compound, [CoCl(NH3)5][KCr(C2O4)3]·0.5H2O (1), has been synthesized and characterized by elemental analysis, IR and electronic spectra, thermal analysis, variable temperature magnetic susceptibility measurements, and single crystal X-ray diffraction. Compound 1 consists of two-dimensional [{KCr(C2O4)3}n]2n− layers, [CoCl(NH3)5]2+ ions and water molecules. Within the 2-D layer, three different types of oxalate coordination modes are present. Each K cation is coordinated by eight oxygen atoms from oxalate groups and also weakly interacts with the ninth oxygen atom. The extensive network of hydrogen bond is formed between the [KCr(C2O4)3]2− layer and the [CoCl(NH3)5]2+ ions. These interactions involve all hydrogen atoms of ammonia ligads and water molecule.

Manganese(II) Oxazolidine Nitroxide Chelates: Structure, Magnetism, and Redox Properties

The mononuclear oxazolidine nitroxide complex [MnII(L•)2](ClO4)2 (1) (L•, 4-dimethyl-2,2-di(2-pyridyl)oxazolidine N-oxide) has been synthesized and investigated using single-crystal X-ray diffraction, variable-temperature magnetic susceptibility measurements, and electrochemistry. The structural analysis reveals bond lengths compatible with a linear L•–MnII–L• arrangement where the ligands are in the neutral ligand form and the central MnII ion is high spin (S = 5/2). Although analysis of the variable-temperature magnetic susceptibility data suggests a strong antiferromagnetic metal–radical interaction, the radical–radical intramolecular interaction could not be determined unambiguously from such fits. The resultant isolated S = 3/2 ground state is confirmed by low-temperature magnetization versus field measurements. Electrochemical studies reveal similar square schemes and redox intermediates to the previously reported analogues [FeII(L•)2][BF4]2 and [CoII(L•)2][NO3]2.