Spin Transition of 1D, 2D and 3D Iron(II) Complex Polymers The Tug-of-War between Elastic Interaction and a Shock-Absorber Effect

Summary.  The structures of linear chain Fe(II) spin-crossover compounds of α,β- and α,ω-bis (tetrazol-1-yl)alkane type ligands are described in relation to their magnetic properties. The first threefold interlocked 3-D catenane Fe(II) spin-transition system, [μ-tris(1,4-bis(tetrazol-1-yl)butane-N1,N1′) iron(II)] bis(perchlorate), will be discussed. An analysis is made among the structures and the cooperativity of the spin-crossover behaviour of polynuclear Fe(II) spin-transition materials. Corresponding author. E-mail: koning@iacgu7.chemie.uni-mainz.de Received April 8, 2002; accepted April 18, 2002     

Derivatives of arylhydrazonic acids. Part 3: Stereochemical rearrangement of Z-oxanilo-N-dialkyl-N-arylamidrazones

Oxanilo-N¹-dialkyl-N²-arylamidrazones have been prepared by nucleophilic substitution of the chloride function of appropriate hydrazonoyl chlorides. Relative stabilities of Z- and E-isomers, calculated with the RHF/6-31G^∗ ab initio method, range between 0.7 and 2.1 kcal/mol. The Z-isomer is detected to be thermodynamically more stable for studied compounds. X-ray structure determination of 2-dimethylamino-N-phenyl-2-phenylhydrazonoacetamide revealed E- and Z-isomers (ratio 1:1) in the crystal. The different intra- and intermolecular hydrogen bond interactions, which are identified in solid state of compounds, are dissolved in polar solvents. All compounds were found to form E/Z-equilibrium in solution. In some cases E-isomers could be separated and fully characterized.     

Improvement of H/V technique by rotation of the coordinate system

In this work we investigate the application of the rotation of the coordinate system before applying denoising techniques aimed at improving the H/V spectral ratio for seismic site effects estimation. By this rotation, one can detect the direction of maximum and minimum matching between any couple of orthogonal H/V ratios. The direction of minimum matching should represent the direction of maximum anisotropy of the surface layer or a directional noise. To further improve the method, singular spectrum analysis and WASEE techniques are then applied.     

Preconcentration of middle oxyethylated nonylphenols from water samples on magnetic solid phase

Magnetic solid phase extraction (MSPE) is proposed as a simple and fast method for the preconcentration of free middle oxyethylated nonylphenols (NPs) from water. Middle oxyethylated NPs were extracted by MSPE from different water samples (10 and 500 ml samples of distilled, potable, well, river and pond water in concentrations of 30 and 0.6 μg ml⁻¹) using magnetically modified polyphenyleneoxide, Tenax TA and Tenax GR as magnetic adsorbents. Recoveries were 80–100% and relative standard deviations were less than 10%.     

Multiple steps and multiple excitations in photoisomerization of azobenzene

Detailed understanding of femtosecond-scale photochemical processes requires dynamical simulations that are complementary to interpretations based on transitions between energy surfaces. For cis to trans photoisomerization of azobenzene following a 100 fs laser pulse, we find that the mechanism is rotation about the central NN bond, and the process is complete in less than 1 ps. The initial excitation and subsequent de-excitation are each achieved via multiple steps, with the molecule always in a superposition of electronic states, as the 3N nuclear degrees of freedom are excited by the laser pulse.     

Sequential synthesis of multiblock copolymers by atom transfer radical and cationic polymerization

ABCBA‐type pentablock copolymers of methyl methacrylate (MMA), styrene (S), and isobutylene (IB) were prepared by a three‐step synthesis, which included atom transfer radical polymerization (ATRP) and cationic polymerization: (1) poly(methyl methacrylate) (PMMA) with terminal chlorine atoms was prepared by ATRP initiated with an aromatic difunctional initiator bearing two trichloromethyl groups under CuCl/2,2′‐bipyridine catalysis; (2) PMMA with the same catalyst was used for ATRP of styrene, which produced a poly(S‐b‐MMA‐b‐S) triblock copolymer; and (3) IB was polymerized cationically in the presence of the aforementioned triblock copolymer and BCl₃, and this produced a poly(IB‐b‐S‐b‐MMA‐b‐S‐b‐IB) pentablock copolymer. The reaction temperature, varied from ?78 to ?25 °C, significantly affected the IB content in the product; the highest was obtained at ?25 °C. The formation of a pentablock copolymer with a narrow molecular weight distribution provided direct evidence of the presence of active chlorine at the ends of the poly(S‐b‐MMA‐b‐S) triblock copolymer, capable of the initiation of the cationic polymerization of IB in the presence of BCl₃. A differential scanning calorimetry trace of the pentablock copolymer (20.1 mol % IB) showed the glass‐transition temperatures of three segregated domains, that is, polyisobutylene (?87.4 °C), polystyrene (95.6 °C), and PMMA (103.7 °C) blocks. One glass‐transition temperature (104.5 °C) was observed for the aforementioned triblock copolymer. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 6098–6108, 2004     

Synthesis and characterization of newberyite

Phosphates belong to the extensive group of inorganic pigments that are very often used in industry of plastics and anticorrosive paints. Also, the powders of newberyite MgHPO₄·3H₂O and α-pyrophosphate Mg₂P₂O₇ can find the usage in this field. Thus, these compounds were the centre of our attention. Newberyite and α-pyrophosphate were synthesized by the method of gelling. Impact of various ways of synthesis, especially reaction conditions, on the structural, thermal, physical and optical properties was investigated. α-pyrophosphate was synthesized by the thermal decomposition of newberyite at temperature around 500°C. Both powders are white color, but the newberyite is the whitest one. The reaction pH particularly affected the particle size distribution and optical properties.     

Electrochemical synthesis of polyfluorinated compounds with functional groups

The electrochemical fluorination of alkanedisulfonyl fluorides, alkanesulfonyl amides and alkanedisulfonyl amides is described. Detailed analysis of the products and the electrolyte and new information on higher nickel fluorides have led to a new insight into the mechanism of electrochemical fluorination. Received: 27 May 1997 / Accepted: 22 October 1997