Coordination versatility of tridentate pyridyl aroylhydrazones towards iron: tracking down the elusive aroylhydrazono-based ferric spin-crossover molecular materials

The two potentially tridentate and monoprotic Schiff bases acetylpyridine benzoylhydrazone (HL(1)) and acetylpyridine 4-tert-butylbenzoylhydrazone (HL(2)) demonstrate remarkable coordination versatility towards iron on account of their propensity to undergo tautomeric transformations as imposed by the metal centre. Each of the pyridyl aroylhydrazone ligands complexes with the ferrous or ferric ion under strictly controlled reaction conditions to afford three six-coordinate mononuclear compounds [Fe(II)(HL)(2)](ClO(4))(2), [Fe(II)L(2)] and [Fe(III)L(2)]ClO(4) (HL = HL(1) or HL(2)) displaying distinct colours congruent with their intense CT visible absorptions. The synthetic manoeuvres rely crucially on the stoichiometry of the reactants, the basicities of the reaction mixtures and the choice of solvent. Electrochemically, each of these iron compounds exhibits a reversible metal-centred redox process. By all appearances, [Fe(III)(L(1))(2)]ClO(4) is one of only two examples of a crystallographically elucidated iron(III) bis-chelate compound of a pyridyl aroylhydrazone. Several pertinent physical measurements have established that each of the Schiff bases stabilises multiple spin states of iron; the enolate form of these ligands exhibits greater field strength than does the corresponding neutral keto tautomer. To the best of our knowledge, [Fe(III)(L(1))(2)]ClO(4) and [Fe(III)(L(2))(2)]ClO(4) are the first examples of ferric spin crossovers of aroylhydrazones. Whereas in the former the spin crossover (SCO) is an intricate gradual process, in the latter the (6)A(1)?(2)T(2) transition curve is sigmoidal with T(?)～280 K and the SCO is virtually complete. As regards [Fe(III)(L(1))(2)]ClO(4), M?ssbauer and EPR spectroscopic techniques have revealed remarkable dependence of the spin transition on sample type and extent of solvation. In frozen MeOH solution at liquid nitrogen temperature, both iron(III) compounds exist wholly in the doublet ground state.     

Spherically symmetric inhomogeneous dust collapse in higher dimensional space-time and cosmic censorship hypothesis

We consider a collapsing spherically symmetric inhomogeneous dust cloud in higher dimensional space-time. We show that the central singularity of collapse can be a strong curvature or a weak curvature naked singularity depending on the initial density distribution.     

Kinetics and Mechanism of Oxidation of 1-Phenylsemicarbazide by Peroxydisulphate

Kinetics of oxidation of 1-phenylsemicarbazide (PSC) by peroxydisulphate ion (PDS) have been carried out where by the pseudo first order condition was verified at large excess of PDS concentration. The rate of the reaction was followed spectrophotometrically, The stoichiometry was found to be 1:1 where 1-phenylazoformamide is the oxidation product. The effect of acidity on the rate of oxidation was investigated for different temperatures. The parameters of activation ΔG*, ΔH* and ΔS* were computed for both hydrogen ion depedent and hydrogen ion independent reaction pathes. A free radical mechanism was proposed.     

Estimation of Mean and Covariance Operator for Banach Space Valued Autoregressive Processes with Dependent Innovations

In this paper we study autoregressive processes of order 1 with values in a separable Banach space it B. Such ARB(1)-processes are defined by the recursion equation

Equivalent moduli of continuity, Bloch’s theorem for pluriharmonic mappings in \mathbb{B}{\kern-8pt}\mathbb{B}^{\boldsymbol n}

In this paper, we first establish a Schwarz?CPick type theorem for pluriharmonic mappings and then we apply it to discuss the equivalent norms on Lipschitz-type spaces. Finally, we obtain several Landau??s and Bloch??s type theorems for pluriharmonic mappings.     

A green and simple method for the synthesis of 2,4,5-trisubstituted-1H-imidazole derivatives using acidic ionic liquid as an effective and recyclable catalyst under ultrasound

Research on Chemical Intermediates - In the current work, an acidic ionic liquid ([{(IMC)-4-OMBH}BIM][HSO4]3) has been utilized as an effective and recyclable catalyst for the synthesis of...     

〈331〉晶向ZnTe单晶的太赫兹辐射-探测性能理论研究

根据光整流效应辐射太赫兹理论,计算了〈331〉晶向ZnTe单晶的太赫兹辐射性能.通过与〈110〉、〈111〉晶向对比,当晶体方位角为0°或180°时,利用〈331〉晶向ZnTe单晶辐射太赫兹信号可以与〈111〉晶向相当,强于〈110〉晶向.利用电光取样原理,计算了〈331〉晶向ZnTe单晶的太赫兹探测性能,通过理论计算为〈331〉晶向ZnTe 晶体有效辐射太赫兹波提供理论依据.     

Effect of Al mole fraction on structural and electrical properties of AlxGa1−xN/GaN heterostructures grown by plasma-assisted molecular beam epitaxy

The effect of Al mole fractions on the structural and electrical properties of Al_xGa_1−xN/GaN thin films grown by plasma-assisted molecular beam epitaxy (PA-MBE) on Si (1 1 1) substrates has been investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), and current-voltage (I-V) measurements. X-ray results revealed that the AlGaN/GaN/AlN was epitaxially grown on Si substrate. By applying Vegard's law, the Al mole fractions of Al_xGa_1−xN samples were found to be 0.11, 0.24, 0.30 and 0.43, respectively. The structural and morphology results indicated that there is a relatively larger tensile strain for the sample with the smallest Al mole fraction; while a smaller compressive strain and larger grain size appear with Al mole fraction equal to 0.30. The strain gets relaxed with the highest Al mole fraction sample. Finally, the linear relationship between the barrier height and Al mole fraction was obtained.     

Eigenvalues and eigenfunctions of discontinuous Sturm--Liouville problems with eigenparameter-dependent boundary conditions

We extend some fundamental spectral properties of classic regular Sturm--Liouville problems to discontinuous boundary-value problems with eigenvalue-dependent boundary conditions. We suggest a new approach for investigation of such type discontinuous problems.     

ON ALGEBRAIC VOLUME DENSITY PROPERTY

A smooth affine algebraic variety X equipped with an algebraic volume form ω has the algebraic volume density property (AVDP) if the Lie algebra generated by complete algebraic vector fields of ω-divergence zero coincides with the space of all algebraic vector fields of ω-divergence zero. We develop an effective criterion of verifying whether a given X has AVDP. As an application of this method we establish AVDP for any homogeneous space X = G/R that admits a G-invariant algebraic volume form where G is a linear algebraic group and R is a closed reductive subgroup of G.