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41.
合成和表征了4种以四溴代邻苯二甲酸根阴离子(4Br-PHTH)桥联、以1,10-菲咯啉(phen),5-硝基-1,10-菲咯啉(NO_2-phen),2,2′-联吡啶(bpy)和4,4′-二甲基-2,2′-联吡啶(Me_2bpy)端接的双核钴(Ⅱ)配合物[Co_2(4Br-PHTH)(L)_4](ClO_4)(L=phen(l),NO_2-phen(2),bpy(3),Me_2bpy(4))。基于IR光谱、元素分析、电导测量等方法推定配合物具有四溴代邻苯二甲酸根桥联结构和Co(Ⅱ)离子具有畸变的八面体配位环境。进行了配合物变温磁化率(75~300K)的测定,其数据已用从自旋哈密顿符导出的磁方程拟合,求得交换参数J=-0.87cm~(-1)(1),-0.84cm~(-1)(2),-0.82cm~(-1)(3),-0.85cm~(-1)(4),表明金属离子间有弱的反铁磁性自旋交换相互作用。 相似文献
42.
Youheng Shi Zhihui Zhang 《Journal of inclusion phenomena and macrocyclic chemistry》1994,18(2):137-147
The interactions ofp-tert.-butylcalix[4]arene bearing polyoxyethylene chains (C3) with pyrene (Py), 1-anilino-8-naphthalenesulfonate (ANS) andN-phenyl-naphthylamine (NPN) in aqueous solution were studied by absorption and fluorescence measurements. Absorption spectral changes and fluorescence enhancements reveal that C3, which has a hydrophobic cavity, can include organic molecules and ions in aqueous solution and form 11 host-guest complexes with ANS and NPN. C3 forms inclusion complexes with Py at different stoichiometries depending on the host: guest molar ratio. Binding constants of 2.2×104, 2.0×104 and 3.6×105 dm3 mol–1 were calculated for the C3Py, C3ANS and C3NPN complexes (11), respectively, based on the Benesi-Hildebrand equation.Author for correspondence. 相似文献
43.
Ch. Krüger H. Schwer J. Karpinski K. Conder E. Kaldis C. Rossel M. Maciejewski 《无机化学与普通化学杂志》1994,620(11):1932-1936
Structural investigations on powder samples of Y2Ba4Cu7O15–x with different carbonate content have been performed. Powder x-ray Rietveld refinements showed the remarkable influence of carbonate incorporation on the lattice parameters. Most important is the decrease of Tc with increasing carbonate content. We assign these effects to an incorporation of the carbonate ion into the crystal lattice, copper vacancies at the Cu(1) position and a possible misorientation of the copper oxygen single chains. No change of the structure (e. g. superstructure) could be found. 相似文献
44.
The conformational properties and elastic behaviors of protein-like single chains in the process of tensile elongation were investigated by means of Monte Carlo method. The sequences of protein-like single chains contain two types of residues: hydrophobic (H) and hydrophilic (P). The average conformations and thermodynamics statistical properties of protein-like single chains with various elongation ratio λ were calculated. It was found that the mean-square end-to-end distance r increases with elongation ratio,λ. The tensor eigenvalues ratio of : decreases with elongation ratio λ for short (HP)x protein-like polymers, however, the ratio of : increases with elongation ratioλ,especially for long (H)x sequence. Average energy per bond increases with elongation ratioλ, especially for(H)x protein-like single chains. Helmholtz free energy per bond also increases with elongation ratioλ. Elastic force (f), energy contribution to force (fU) and entropy contribution to force (fs) for different protein-like single chains were also calculated.These investigations may provide some insights into elastic behaviors of proteins. 相似文献
45.
Yano M Taketsugu T Hori K Okamoto H Takenaka S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(16):3991-3999
The series of alkyl 4-[2-(perfluorooctyl)ethoxy]benzoates (F8-n) shows a systematic change of crystal structures depending on the length of the alkyl chain: separate packing of perfluorooctyl (Rf) and alkyl (Rh) chains from each other for shorter (n=2) and longer (n=11) members, alternate packing of Rf and Rh chains for middle (n=6,7) members, and an intermediate type of packing for n=4. Semiempirical MO calculations show slightly repulsive interactions between the Rf chains, and attractive ones between Rf and Rh chains and between Rh and the core of a molecular pair. It is concluded that fluorination determines the molecular shape of the crystal structures by making the chain rigid. It is confirmed that the interactions between Rf chains are small compared with those between other moieties and that they are forced to aggregate owing to the exclusion from other moieties. Thus, the effect is dependent on the geometries and intermolecular interactions of the other moieties. 相似文献
46.
Grzegorz Schroeder Bogumi
Brzezinski Dariusz Pod
bski Eugeniusz Grech 《Journal of Molecular Structure》1997,416(1-3):11-19
Deprotonation of 5,10,15,20-tetrakis(pentafluorophenyl)-21-H, 23-H-porphyrin (PhF5PorH2) by various bases has been studied by 1H NMR and kinetic methods. The kinetic parameters in acetonitrile were defined for proton transfer reactions yielding [NH]+ protonated bases and [NHN]− anions with intramolecular hydrogen-bonded chains. 相似文献
47.
A new copper(Ⅱ) compound with imino nitroxide radicals [Cu(IM-MeImz)2]·(SCN)2 (IM-meImz =2-(5-methylimidazol-4-yl)-4,4,5,5-tetramethyl-2-imidazoline-1-oxyl) has been synthesized and characterized structurally and magnetically. It crystallizes in monoclinic, space group P21/c with a = 9.3604(7), b = 10.3012(7), c = 16.6684(12) (A), β = 105.0290(10)°, V = 1552.25(19)(A)3, C24H34CuN10O2S2, Mr = 622.27, Z = 2, Dc = 1.331 g/cm3, μ(MoKα) = 0.876 mm-1, F(000) =650, the final R = 0.0374 and wR = 0.1079. X-ray analysis demonstrates that the IM-MeImz ligand is coordinated to the copper(Ⅱ) ion as an unusual didentate chelate with a κ2 N(MeImz),O(IM) mode in the complex. The square-planar coordination sites at Cu(Ⅱ) are occupied by two O and two N atoms from the imino nitroxide radicals. The complex molecules are connected as a onedimensional polymer structure by intermolecular interactions. Magnetic measurements show that there are intramolecular antiferromagnetic interactions between the Cu(Ⅱ) ion and radicals. 相似文献
48.
Anab initio crystal orbital method is used to calculate the energies of an infinite chain of H atoms and of linear arrangements of H2 molecules with different interatomic distances. The H2 arrangements are not stable in respect to isolated molecules. The cohesive energy of an optimized arrangement of H atoms chain is 0.0354 a.u. 相似文献
49.
Dynamic surface elasticity of polymer solutions 总被引:1,自引:0,他引:1
B. A. Noskov 《Colloid and polymer science》1995,273(3):263-270
The surfaces of surfactant solutions exhibit viscoelastic dilational behavior which may be investigated by modern optical and mechanical methods. The present study focuses on the dynamic dilational properties of the polymer solution — gas interface. Linear flexible polymer chains at the surface are considered as consisting of trains, lying on the surface, and loops and tails that protrude into the liquid. The Rouse model is used to describe the inner dynamics of the trains, whereas their motion relative to their neighbors on the surface can be described with the help of the reptation conception. An expression for the complex dynamic dilational surface elasticity has been derived. Although, in general, the relaxation of the surface tension is characterized by an infinite series of relaxation times, it is shown that for many systems the dynamics of the surface layer can be described approximately by only two main relaxation times. The dispersion equation, which was obtained earlier for solutions of conventional surfactants, is shown to be fulfilled for polymer solutions also. 相似文献
50.
Min-zhi Chen Xiao-liang Wang Fang-fang Tao Qi Xue Ping-chuan 《高分子科学》2007,(1):107-111
The concept of entanglement provides the basis of our current understanding of the flow behavior of polymer melts, Current techniques developed to investigate the degree of interpenetration of polymer chains only provide indirectly the information of the degree of entanglement in a relatively large scale (several to tens of nanometer). In this article, we report ^1H-NMR spectroscopy with dipolar filters under fast magic angle spinning for probing chain interpenetration of polymer glasses at the molecular level. 相似文献