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381.
Making use of the invariant property of the equilibrium size distribution of the hydrogen bonding clusters formed in hydrogen bonding system of AaDd type, the analytical expressions of the free energy in pregel and postgel regimes are obtained. Then the gel free energy and the scaling behavior of the number of hydrogen bonds in gel phase near the critical point are investigated to give the corresponding scaling exponents and scaling law. Meanwhile, some properties of intermolecular and intramolecular hydrogen bonds in the system, sol and gel phases are discussed. As a result, the explicit relationship between the number of intramolecular hydrogen bonds and hydrogen bonding degree is obtained. 相似文献
382.
基于氢键的形成和缩聚反应机理在统计意义下的相似性 ,利用高分子反应统计理论和反应动力学理论对氢键溶液的一个模型体系进行了相关讨论 .给出了体系的溶胶分数和发生溶胶 -凝胶相变的条件 ,指出质子受体基团间的竞争作用对溶胶凝胶相变点的影响 ,进而讨论了体系的数量分布函数和相关问题 . 相似文献
383.
384.
R. Lefebvre 《International journal of quantum chemistry》1983,23(2):543-550
A self-consistent field approximation allowing for a change of coordinates is applied to a model of two coupled oscillators considered by Davis and Heller [J. Chem. Phys. 75 , 246 (1981)]. The model accounts well for the unsymmetrical nonstationary states involved in the quantum dynamical tunneling phenomenon. 相似文献
385.
Bismuth silicate nanopowders were prepared by the sol-gel method. Tetraethyl orthosilicate (TEOS) and Bi2O3 were used as the starting materials. The precursors were heat-treated at 750℃ for 2 h. The size distribution of Bi4Si3O12 nanopowders is 40~100 nm. The TG-DTA curves, the XRD patterns and the TEM microphotograph of Bi4Si3O12 are discussed. Compared with crystal materials, the excitation spectra and the emission spectra of Bi4Si3O12 nanopowders indicate blue shift. 相似文献
386.
The coordination chemistry of 6-methylpyridine-2-methanol (1) and enantiopure (R)-1-(6-methylpyridin-2-yl)ethanol (2) with a range of divalent first-row transition metal salts has been investigated in an effort to determine whether hydrogen-bonded helicates will form, as observed for cobalt(II) salts. Hydrogen-bonded helicates, [Cu2(1)2(1-H)2X2] (X = Cl, Br), were only observed upon combining 1 with CuCl2 and CuBr2 in MeOH solution. Other metal salts led to alternative products, viz. Cu(ClO4)2 in the presence of base gives [Cu2(1)2(1-H)2](ClO4)2, ZnCl2 and ZnBr2 give the 1-D helical coordination polymers [Zn(1-H)Cl]infinity and [Zn(1-H)Br]infinity, a mixture of NiCl2 and Ni(OAc)2 produces the [Ni4(1-H)4Cl2(OAc)2(MeOH)2] cubane, NiCl2 leads to the [Ni4(1-H)4Cl4(MeOH)4] cubane, while MnCl2 gives the known cubane [Mn4(1-H)6Cl4]. The reaction of 2 with CuCl2 produces the mononuclear complex Lambda-[Cu(2)2Cl]Cl, while reaction with CuBr2 leads to a dimer, Lambda,Lambda-[Cu2(2)3(2-H)Br2]Br, which is held together by a single hydrogen bond between the monomeric subunits. The solid-state CD spectra of these latter complexes were recorded and found to be very similar. The temperature-dependent magnetic behavior of [Cu2(1)2(1-H)2X2] (X = Cl, Br), [Cu2(1)2(1-H)2](ClO4)2, [Cu2(2)3(2-H)Br2]Br, and [Ni4(1-H)4Cl2(OAc)2(MeOH)2] was investigated. Weak antiferromagnetic coupling between the copper(II) centers is mediated by the hydrogen bonds in the [Cu2(1)2(1-H)2X2] (X = Cl, Br) complexes. 相似文献
387.
Raturi R Lefebvre J Leznoff DB McGarvey BR Johnson SA 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(2):721-730
The reaction of P(CH2OH)3 with methyl anthranilate NH2C6H4-2-CO2Me produced the ligand precursor P(CH2NHC6H4-2-CO2Me)3 (1). The reaction of 1 with [Y{N(SiMe3)2}3] produced hexadentate yttrium complex [Y{P(CH2NC6H4-2-CO2Me)3}] (2), in which the metal centre is coordinated by three amido donors and the three carbonyl oxygen atoms of the ester groups. The 31P{1H} NMR spectrum features 1J Y,P=15 Hz, and DFT calculations demonstrate that through-space interaction between the minor lobe of the phosphine lone pair and the yttrium centre allows a large Fermi contact contribution to this spin coupling constant. The EPR spectrum of the analogous paramagnetic Gd complex [Gd{P(CH2NC6H4-2-CO2Me)3}] (3) can be modelled by using a B20 crystal field parameter of +/-0.19 cm(-1). Heterodinuclear complexes were prepared by the reactions of 1 and 3 with [5,10,15,20-tetrakis(4-methoxyphenyl)porphinato]cobalt(II), by binding of the phosphine lone pair to the d(7) cobalt centre. The solid-state EPR spectrum of the heterodinuclear yttrium complex 4 exhibits large superhyperfine coupling to the phosphorus nucleus, indicative of an S=1/2 complex in which the unpaired electron resides in the cobalt dz2 orbital directed at the phosphine donor. The magnetic susceptibility of the heterodinuclear Gd-Co complex 5 demonstrates that through-space antiferromagnetic coupling occurs between unpaired electrons on the gadolinium and cobalt centres. 相似文献
388.
Nicolas Merle Morad Nayer Erwan Le Roux Frédéric Lefebvre Jean Thivolle-Cazat 《Journal of organometallic chemistry》2008,693(10):1733-1737
The interaction of [W(C-tBu)(CH2-tBu)(OAr)2] (Ar = 2,6-iPr2C6H3) (1), with the hydroxyl groups of a silica dehydroxylated at 700 °C leads to [(SiO)W(OAr)2(C-tBu)] (2) which was characterized by IR, solid-state NMR and mass balance analysis. This well-defined surface species is an efficient catalyst for the metathesis of pent-2-yne. 相似文献
389.
390.
采用真空热蒸发方法制备了有机单体薄膜对硝基苯腈p-nitrobenzonitrile(PNBN).利用扫描隧道显微镜(STM)在PNBN薄膜上进行信息记录点的写入,通过在STM针尖和高定向裂解石墨(HOPG)之间施加电压脉冲,直接观察到了信息记录点写入前后薄膜发生的局域结构转变.信息记录点的写入机制主要是这种纳米范围结构变化所导致的薄膜由高阻态向低阻态转变,高阻态对应0,低阻态对应1.
关键词:
p-nitrobenzonitrile(PNBN)
扫描隧道显微镜(STM)
结构转变 相似文献