Accessibility and Selective Stabilization of the Principal Spin States of Iron by Pyridyl versus Phenolic Ketimines: Modulation of the (6)A(1) ↔ (2)T(2) Ground-State Transformation of the [FeN(4)O(2)](+) Chromophore

Several potentially tridentate pyridyl and phenolic Schiff bases (apRen and HhapRen, respectively) were derived from the condensation reactions of 2-acetylpyridine (ap) and 2'-hydroxyacetophenone (Hhap), respectively, with N-R-ethylenediamine (RNHCH(2)CH(2)NH(2), Ren; R = H, Me or Et) and complexed in situ with iron(II) or iron(III), as dictated by the nature of the ligand donor set, to generate the six-coordinate iron compounds [Fe(II)(apRen)(2)]X(2) (R = H, Me; X(-) = ClO(4)(-), BPh(4)(-), PF(6)(-)) and [Fe(III)(hapRen)(2)]X (R = Me, Et; X(-) = ClO(4)(-), BPh(4)(-)). Single-crystal X-ray analyses of [Fe(II)(apRen)(2)](ClO(4))(2) (R = H, Me) revealed a pseudo-octahedral geometry about the ferrous ion with the Fe(II)-N bond distances (1.896-2.041 ?) pointing to the (1)A(1) (d(π)(6)) ground state; the existence of this spin state was corroborated by magnetic susceptibility measurements and M?ssbauer spectroscopy. In contrast, the X-ray structure of the phenolate complex [Fe(III)(hapMen)(2)]ClO(4), determined at 100 K, demonstrated stabilization of the ferric state; the compression of the coordinate bonds at the metal center is in accord with the (2)T(2) (d(π)(5)) ground state. Magnetic susceptibility measurements along with EPR and M?ssbauer spectroscopic techniques have shown that the iron(III) complexes are spin-crossover (SCO) materials. The spin transition within the [Fe(III)N(4)O(2)](+) chromophore was modulated with alkyl substituents to afford two-step and one-step (6)A(1) ? (2)T(2) transformations in [Fe(III)(hapMen)(2)]ClO(4) and [Fe(III)(hapEen)(2)]ClO(4), respectively. Previously, none of the X-salRen- and X-sal(2)trien-based ferric spin-crossover compounds exhibited a stepwise transition. The optical spectra of the LS iron(II) and SCO iron(III) complexes display intense d(π) → p(π)* and p(π) → d(π) CT visible absorptions, respectively, which account for the spectacular color differences. All the complexes are redox-active; as expected, the one-electron oxidative process in the divalent compounds occurs at higher redox potentials than does the reverse process in the trivalent compounds. The cyclic voltammograms of the latter compounds reveal irreversible electrochemical generation of the phenoxyl radical. Finally, the H(2)salen-type quadridentate ketimine H(2)hapen complexed with an equivalent amount of iron(III) to afford the μ-oxo-monobridged dinuclear complex [{Fe(III)(hapen)}(2)(μ-O)] exhibiting a distorted square-pyramidal geometry at the metal centers and considerable antiferromagnetic coupling of spins (J ≈ -99 cm(-1)).     

N‐(4‐Methoxy­benzyl­idene)‐N′‐(2‐pyridyl)­hydrazine

Molecules of the title compound (alternative name p‐methoxybenzaldehyde 2‐pyridyl­hydrazone), C₁₃H₁₃N₃O, adopt an E configuration about the azomethine C=N double bond. Molecules are almost planar, the dihedral angle between the pyridine and methoxy­phenyl rings being only 6.19 (12)°. Pairwise N—H⃛N hydrogen bonds [R(8) in graph‐set notation] link centrosymmetrically related mol­ecules into discrete pairs.     

Spectral and Electrical Properties of a Medium Pressure,Low-Power,RF-Generated Postdischarge Nitrogen Plasma Jet

A method for obtaining a medium pressure (p ～ 1 torr), low power (< 100 W), RF-generated plasma jet, suitable for chemical kinetics studies and technological applications is described. Though various supply gases can be used to create the plasma jet, only results on the properties of a nitrogen jet are given in this paper with an emphasis on some spectral and electrical characteristics. The emission spectra of the nitrogen jet are discussed and spatial distributions of the relative concentration of nitrogen or radical impurities emitting species such as N₂(C³Π_u, v' = 0), NH(A³Π_g, v'=0) in the bulk of the postdischarge plasma are calculated from the intensity of their vibrational bands. Electrical space resolved double probe measurements and the spatial distributions of the electron density and temperature in the plasma jet are also presented. Possible applications are shortly discussed.     

Measurement of the decay rate and the parameter αK* of the decay KL → μμγ

The rate of the decay of the neutral K meson into K _L ⁰ → μμγ has been measured with the NA48 detector at the CERN SPS. A total of 59 events has been observed with an estimated background of 14 events. The overall Kaon flux was determined to be 1.2 × 10⁹. This observation corresponds to a branching ratio of (3.4 ± 0.6_stat ± 0.4_sys × 10^-7. Using this branching ratio the parameter α_K* describing the relative strength of the two contributing amplitudes to this decay, through intermediate pseudoscalar or vectorlike mesons, was measured to be α_K* = -0.04+ _-0.21 ^+0.24 .     

Electronic transitions in Li4CoCl4.10H2O

The electronic spectrum of Li₄CoCl₆.10H₂O was recorded at liquid nitrogen temperature in the 4,000–25,000 cm^?1 spectral region. The simi larity of this spectrum to that of CoCl₂ permitted us to assume O_h syn metry of the [CoCl₆]^4? cluster in our sample. The band assignment was performed in the crystal field approximation using Tanabe and Sugano's energy matrices for Dq = 730 cm^?1, B = 820 cm^?1 and C/B = 4.4.The large number of bands and high intensity of the maxima in the regio 19,000–21,000 cm^?1 is discussed.     

Oxides of 3-methyl-1,2,4-benzotriazine

The previously prepared 3-methyl-1,2,4-benzotriazine oxide¹ is shown to be the 4-oxide 5. Synthesis and structures of other isomeric and related oxides are described. A modification of a previously described synthesis of 1,2,4-benzotriazines produces purer products in higher yields.     

EFFECT OF THE COMPOSITION OF m-CRESOL/H2O SOLVENT ON HYDRODYNAMIC PROPERTIES OF NYLON 6

The intrinsic viscosity [ η], Huggins constant (KH), [ η]0, α3 and flow activation energy values of nylon 6 have been measured in water/m-cresol (0/100-20/80) systems at different temperatures (20-60℃). It has been found that the intrinsic viscosity, [η]0 and α3 increase with the increase in water contents in m-cresol up to 15% and then decrease. They increase with the increase in temperature irrespective of solvent composition. It has been noted that the percent increase of α3 is the highest at 60℃ and the lowest at 20℃ for a particular solvent system. The intrinsic viscosity data obey Arrhenius equation over the considered conditions. The activation energy and the KH values decrease very sharply with the addition of water,giving a minimum value at 15% of water and then increase slowly. The variation of all the parameters has been explained in terms of variation in thermodynamic quality of solvent with the addition of water to m-cresol and change in temperature,resulting in the change of conformational and orientational properties of polymer molecules. This change of solvent quality also results in variation of selective sorption of solvent over the polymer, such as hydrogen bonding, etc.     

On Stability of $L$-Fuzzy Mappings with Related Fixed Point Results

In this paper, a general idea of Presic type $L$-fuzzy fixed point results using some weakly contractive conditions in the setting of metric space is initiated. Stability of $L$-fuzzy mappings and associated new concepts are proposed herein to complement their corresponding notions related to crisp multi-valued and single-valued mappings. Illustrative nontrivial examples are provided to support the assertions of our main results.     

Oxiranyl β-aminovinyl ketones. 5. Transformation of 2-methyl-2-(1-halogenoalkyl)-3(2h)-furanones into oxiranyl β-aminovinyl ketones

In reaction with amines 2-methyl-2-(1-halogenoalkyl)-3(2H) furanones form S-amino-1-halogeno-3-hydroxy-2-methyl-4 penten-3-ones and 6-amino-2-halogeno-3-hydroxy-3-methyl-5-hexen-3-ones, which are converted by the action of bases into the corresponding oxiranyl -aminovinyl ketones.Belorussian State University, Department of Organic Chemistry and Chemistry of High-Molecular Compounds, Minsk. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 609-612, May, 1995. Original article submitted April 11, 1995.