{[Gd(DMF)_3(DMSO)(H_2O)_3](μ-CN)[Fe(CN)_5]}·2H_2O的合成,结构表征和磁性(英文)

0IntroductionThefirstmolecule鄄basedmagnetswerereportedin1986[1].Duringthelasttwodecades,moreandmoreattentionhasbeenpaidtothesynthesisofmolecule鄄basedmagnets,especiallytoPrussianBlueanalogu鄄es[2].TheoldPrussianBlueanalogueshavebeenbroughtuptodateduetoth…     

Novel conjugated polymer poly(benzobisoxazole-2,6-diylvinylene): synthesis and evidence of aggregate formation in methanesulfonic acid

A new conjugated polymer poly(benzobisoxazole-2,6-diylvinylene) (PBOV) has been synthesized as an analogue of poly(p-phenylene benzobisoxazole) (PBO). The comparison between PBOV and PBO has been carried out by Fourier transform infrared spectroscopy, thermogravimetric analysis, UV, and photoluminescence (PL) spectroscopy. The UV absorption peaks, PL excitation and emission wavelengths of PBOV have a significant red-shift due to the better electronic delocalization. Similar to PBO, it can be observed in the PL spectra of PBOV at various concentrations in methanesulfonic acid (MSA) that the intensity of emission was depressed and the highly structured emission spectra gradually changed to featureless, red-shifted, and broad spectra with increasing concentration. The change in emission spectra can be attributed to the existence of the interchain aggregates, although PBOV does not show highly ordered structure as PBO does.     

Polymeric Pd catalysts for the reduction of acetamidocinnamic acid azlactone and its solvolysis products

Pd complexes have been obtained from linear and cross-linked copolymers ofR,S-, R-, andS-1-(4-vinylphenyl)ethylamine (1) with styrene and divinylbenzene. Reduction of these compounds gave catalysts which were active in the reductive solvolysis of -acetaminocinnamic acid azlactone (2) and hydrogenation of the solvolysis products -acetamidocinnamic acid (ACA), its esters, and its 1-phenylethylamide. The catalysts showed no enantioselective properties in the reductive hydrolysis, but were more active than the catalyst obtained in the absence of the polymer (the monomeric analog). The use of polymeric catalysts has shown that, in reductive aminolysis, the chiral nucleophile plays the dominant part in determining the stereoselectivity of the reaction, rather than the chiral ligand of the catalytic complex. The polymer matrix stabilizes the low-valent state of the palladium in the complex. In the hydrogenation of ACA and its esters, the catalyst on the cross-linked polymer is much more active than its monomeric analog, but showed no enantioselectivity. Hydrogenation of acetamidocinnamic acidR-andS-1-phenylethylamides on a chiral Pd-polymer catalyst occurred with double asymmetric induction.Deceased.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow. A. V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, 117912 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 10, pp. 2368–2380, October, 1992.     

介质对配合物稳定性的影响——Ⅱ.Cu(SCN)+—NaNO3—二氧六环—水体系

本文用分光光度法确定了25℃时配阳离子Cu(SCN)~+在NaNO_3—二氧六环—H_2O介质中的稳定常数。溶剂组成变化范围为0,5,10,15和20wt％二氧六环,离子强度范围为0.2～3.0moledm~(-3),溶液的pH=1.5～1.6。本文提出了基于Pitzer方程式的最小二乘多项式逼近法,确定出各种不同组成混合溶剂中配合物的热力学稳定常数。讨论了该常数和一级介质效应与溶剂组成和介电常数的关系。     

Synthesis and polymerisation of α,ω-bis(3-pyrrolyl)alkanes

The synthesis, characterisation and polymerisation studies of a homologous series of α,ω-bis(pyrrolyl)alkanes are described. These α,ω-bis(pyrrolyl)alkanes were produced using Friedel-Crafts acylation followed by reduction of the carbonyl group using Red-Al^®. Chemical polymerisation of the resultant dimers using FeCl₃ produced poly(α,ω-bis(pyrrolyl)alkane) films, which were characterised by SEM, FTIR and tested for conductivity.     

Preparation of holographic gratings of liquid crystals dispersed in polyurethane acrylates under controlled reaction conditions.

Transmission gratings of holographic polymer-dispersed liquid crystals (HPDLC) are prepared under controlled reaction conditions by adding various amounts of chain-transfer agent (CTA). The resulting films have a higher gel content with lower cross-link density, less dark reaction, less grating shrinkage with much smoother LC/polymer interfaces, smaller induction period, and fast saturation of diffraction efficiency, which shows a maximum of 95 % with 1 % CTA. An optimum LC content of 35 % is verified on the basis of morphology and reaction kinetics.     

New ferrocene-containing structures: Poly(silyl ester)s

Two new polymeric structures containing ferrocene units along the chains, namely poly(silyl ester)s, have been synthesized and characterized: a geminal poly(silyl ester) (g-PSE) and one having a disiloxane spacer between the silyl ester groups (s-PSE). The condensation polymerization of AA/BB monomer systems in solution was used in both cases as preparation method involving a silicon-containing diol, (diphenylsilane diol or 1,3-bis(hydroxy)-tetramethyldisiloxane), and 1,1′-di(chlorocarbonyl)ferrocene. The polymers were investigated by differential pulse voltammetry in order to evaluate the redox behavior. Due to the presence of the silyl ester groups in the chain, these polymers are hydrolytically degradable.