粉状白钨酸的研究——ⅩⅤ.利用粉状白钨酸的离子交换性能直接制备一价阳离子的十聚钨酸盐

以粉状白钨酸为原料,利用它的离子交换性能制得了碱金属及铵的酸式十聚钨酸盐M_3HW_(10)O_(32)·11H_20(M=NH_4、Li、Na、K)。测定了它们的差热分析、X-射线粉末衍射、IR和UV光谱,在水溶液中的稳定性以及光致变色等性质。     

某些有机胺十聚钨酸盐在溶液中的稳定性研究

研究了3种有机胺十聚钨酸盐在某些有机溶剂及水中的稳定性,通过元素分析、红外光谱及紫外吸收光谱对转化产物进行了鉴定,以期有助于对其光致变色性质作较深入的研究。     

DMF和DMSO配位的金属十聚钨酸盐在非水溶剂中光致变色性质的研究

研究了某些DMF和DMSO配位的金属十聚钨酸盐在 3 种有机溶剂中的光致变色性质,通过ESR、NMR和可见吸收光谱的研究及对五价钨的测定,说明了光致变色性质的产生与金属阳离子无关,而取决于十聚钨酸根W₁₀O₃₂^4-、金属离子的配体及所采用溶剂。     

粉状白钨酸的研究(Ⅻ)——某些聚钨酸有机铵盐的合成和性质

以粉状白钨酸和三种有机铵--乙二胺、乙醇胺和异丙胺为原料,分别合成了偏钨酸盐和仲钨酸盐。通过紫外,红外光谱、核磁共振谱以及极谱测定,研究了三种不同类型有机胺聚钨酸盐的组成与性质,发现乙醇胺和异丙胺的偏钨酸盐具有光敏性。     

含席夫碱基的螺吡喃双功能光致变色材料的合成及性质

设计合成了一系列含席夫碱基的螺吡喃双功能光致变色材料4a~4n. 通过1H NMR, IR和HRMS对其结构进行了表征. 研究了化合物在几种溶剂和PMMA膜中的光致变色性质, 研究了化合物4a在甲醇中, 以及化合物4a和4f在高分子介质聚甲基丙烯酸甲酯(PMMA)中的消色过程. 结果表明, 化合物4e在PMMA膜中光照后呈现出与其它化合物不同的颜色, 为罕见的绿色. 化合物4a在二氯甲烷溶液中有良好的荧光性能. 所合成的新型含席夫碱基的螺吡喃双功能光致变色材料在甲醇、二氯甲烷和环己烷溶液中及在PMMA膜中均表现出良好的光致变色性质.     

粉状白钨酸的研究——ⅩⅫ.六聚钨酸二甲基亚砜加合物的制备

1968年,Fuchs等首次用控制水解法从WO(CH_3)_4中获得了六聚钨酸盐,它的阴离子W_6O_(19)~(2-)结构也已被测定。迄今六钨酸盐主要还是局限于几个多碳有机胺盐。以粉状白钨酸为原料,在二甲基亚砜(DMSO)中制得了一系列DMSO配位的多价金属的六钨酸盐晶体,并测定了其中部分盐类的晶体结构。但六聚钨酸仍未     

粉状白钨酸研究(ⅩⅨ)——聚乙烯醇水溶液中十聚钨酸的稳定性和光化学还原

粉状白钨酸在含聚乙烯醇的水溶液中能够形成十聚钨酸,通过紫外-可见吸收光谱、顺磁共振、pH滴定及五价钨的测定对十聚钨酸的稳定性和光致变色性质进行了研究,结果表明,十聚钨酸的还原程度与溶液的酸度有关,在较高的pH条件下形成单电子还原物种,而在较低的pH条件下则主要形成双电子还原物种.     

WO_3/4,4'-联苄胺光致变色超晶格薄膜的研究

无机 -有机超晶格薄膜材料的制备以及性质研究是目前国际上的研究热点。基于超分子化学自组装原理 ,利用自组装技术构建含有有机分子的光致变色纳米超晶格薄膜材料 ,是一种研制光致变色功能薄膜材料的新方法。此项研究能够为研制变色响应速度快的、稳定性好的、变色可调控的光致变色器件奠定基础 ,具有深远的意义和重要的科学价值。本文采用溶液中相反电荷聚电解质自组装的方法 ( PEs法 ) [1] ,制备了 WO3/4,4′-联苄胺超晶格薄膜 ;采用紫外可见吸收光谱和小角 X-射线衍射谱对薄膜的层状结构和分子的排列方式进行了研究。1　实验部分1.1　…     

十聚钨酸/聚乙烯醇导电膜的制备

最近发现粉状白钨酸在聚乙烯醇(PVA)或其它高分子水溶液中有相当大的溶解度,可以得到稳定的十聚钨酸溶液,并进而得到含十聚钨酸的高分子薄膜。通过光谱鉴定和组成分析,证明了在聚乙烯醇存在下,十聚钨酸能以固态形式存在,而且这是首例十聚钨酸/高分子复合物,并且还研究了组成、湿度、光致变色对复合物薄膜导电性的影响。     

粉状白钨酸研究(ⅩⅠⅩ)——聚乙烯醇水溶液中十聚钨酸的稳定性和光化学还原

粉状白钨酸在含聚乙烯醇的水溶液中能够形成十聚钨酸，通过紫外－可见吸收光谱、顺磁共振、ｐＨ滴定及五价钨的测定对十聚钨酸的稳定性和光致变色性质进行了研究，结果表明，十聚钨酸的还原程度与溶液的酸度有关，在较高的ｐＨ条件下形成单电子还原物种，而在较低的ｐＨ条件下则主要形成双电子还原物种．     

Studies on solid-state proton transfer along hydrogen bond of pyrazolone-ring

Evidence from the time-dependent UV-vis reflection spectra studies indicates the compound 1-phenyl-3-methyl-4-(4-methylbenzal)-5-pyrazolone 4-ethylthiosemicarbazone (PM4MBP-ETSC) undergoes a solid-state photochromism. The reaction rate constant was studied by the first-order kinetics curves. X-ray single crystal structural analysis shows that the pyrazolone-ring stabilizes in the keto form. The conclusion can be made that its photochromism in crystalline is associated with a photoinduced proton transfer reaction (inter- and intra-molecular hydrogen transfer) along hydrogen bond leading to a colored tautomer as the compound crystallizes in H-bonded supramolecular configuration.     

Photoelectrochromic cell with a Ag–TiO2 nanocomposite: Concepts of drawing and display modes

A photoelectrochromic cell is fabricated with a transparent working electrode coated with a Ag–TiO₂ nanocomposite, which exhibits multicolor photochromism, a silver counter electrode, and an electrolyte containing silver ion. When the electrodes are short-circuited (drawing mode), the Ag–TiO₂ coating is active in photochromism, whereas the activity is substantially suppressed, when the cell is open-circuited (display mode). The cell can be initialized by applying a voltage (−1.0 V).     

Raman study of a liquid crystalline gel consisting of photochromic 4‐methyl‐N‐(4‐n‐heptyloxysalicylidene)aniline and a gelling agent (R,R′)‐1,2‐bis(dodecanoylamino)cyclohexane

A liquid crystalline physical gel has been prepared from the mixture of a nematic liquid crystal and a low molecular mass gelling agent containing a hydrogen‐bonding moiety. The newly synthesized liquid crystalline compound exhibited photochromism in the crystalline solid phase. Although photochromism was not observed in the nematic gel state of the mixture, the lifetime of photochromism in the solid phase became longer, compared with that of a single liquid crystalline compound. Some Raman bands of the mixture showed a marked change in both intensity and frequency through the phase transitions. These bands have been assigned to the vibrational modes related to the core part of molecule.     

Mechanism of [gamma-H2SiV2W10O40](4-)-catalyzed epoxidation of alkenes with hydrogen peroxide

The mechanism of [gamma-H2SiV2W10O40]4--catalyzed epoxidation of alkenes with hydrogen peroxide in acetonitrile/tert-butyl alcohol was investigated. The negative Hammett rho+ (-0.88) for the competitive oxidation of p-substituted styrenes and the low XSO (XSO = (nucleophilic oxidation)/(total oxidation)) value of <0.01 for the [gamma-H2SiV2W10O40]4--catalyzed oxidation of thianthrene-5-oxide reveal that the strong electrophilic oxidant species is formed on [gamma-H2SiV2W10O40]4- (I). The preferable formation of trans-epoxide for the epoxidation of 3-substituted cyclohexenes shows the steric constraints of the active oxidant on I. The 51V NMR, 183W NMR, and CSI-MS spectroscopy show that the reaction of I with hydrogen peroxide leads to the reversible formation of a hydroperoxo species [gamma-HSiV2W10O39OOH]4- (II). The successive dehydration of II forms III, which possibly has an active oxygen species of a mu-eta2:eta2-peroxo group. The kinetic and spectroscopic studies show that the present epoxidation proceeds via III. The energy diagram of the epoxidation with density functional theory (DFT) supports the idea.     

Extractive separation of molybdenum as Mo(V) xanthate from Iron, vanadium, Tungsten, copper, uranium and other elements

A simple and selective extraction of molybdenum is described. Tungsten is masked with tartaric acid and molybdenum(VI) is reduced in 2M hydrochloric acid by boiling with hydrazine sulphate. Iron, copper and vanadium are then masked with ascorbic acid, thiourea and potassium hydrogen fluoride respectively. The molybdenum(V) is extracted as its xanthate complex into chloroform, from 1M hydrochloric acid that is 0.4M potassium ethyl xanthate. The complex is decomposed by excess of liquid bromine, and the molybdenum is stripped into alkaline hydrogen peroxide solution. The molybdenum is then determined by standard methods. Large amounts of Cu(II), Mn(II), Fe(III), Ti(IV), Zr, Ce(IV), V(V), Nb, Cr(VI), W(VI), U(VI), Re(VII) and Os(VIII) do not interfere. Several synthetic samples and ferromolybdenum have been rapidly and satisfactorily analysed by the method.     

Dioxotungsten 1,2-benzenedithiolate complex stabilized by NH...S hydrogen bonds

Novel dioxo-tungsten(VI) bis(1,2-benzenedithiolate) complexes with neighboring amide groups, as models for tungsten enzymes, (NEt4)2[W(VI)O2{1,2-S(2)-3,6-(RCONH)2C6H2}2] (R = CH3, t-Bu), were designed and synthesized. The presence of the NH...S hydrogen bond was confirmed through IR spectrometry and X-ray crystallographic analysis. In the W(VI)O2 complexes, the NH...S hydrogen bond trans to the oxo ligand is stronger than that cis to oxo. On the basis of comparisons with [W(VI)O2(1,2-S2C6H4)2](2-), the NH...S hydrogen bond positively shifted the W(VI)/W(V) redox potentials and depressed the reduction by benzoin or triphenylphosphine. These results suggest that the NH...S hydrogen bond stabilizes the oxo ligand through trans influence and regulates O-atom transfer in tungsten and molybdenum enzymes.     

二乙酰丙酮氧钒与γ-甲基吡啶配位化合物的晶体结构

用X射线单晶衍射方法测定了二乙酰丙酮氧钒与γ-甲基吡啶加合物VO(CH_3COCHCOCH_3)_2·NC_5H_4CH_3的晶体结构.晶体属空间群Cm(C_8~3),晶胞参数α=8.288(3)A,b=13.983(7)A,c=11.459(4)A,β=138.32(2)°,Ζ=2.由SYNTEX R3型四圆衍射仪收集了876个独立衍射数据,以Patterson重原子法导出粗结构,经块矩阵最小二乘法修正,最终得偏离因子R=0.093.所得结果与相应吡啶1∶1加合物的分子结构参数进行了对比,探讨了VO(acac)_2·L型这类化合物的结构化学特点,并对第六位配键的键型进行了分析和讨论.     

Photochromism of organometallic compounds with structural rearrangement

This article introduces photochromic properties together with structures of organometallic compounds that undergo photo-induced structural rearrangement. The aim of this review is to survey the research on photochromism by using organometallics which possess by their own nature the properties responsible for the photochromism such as bonding and structural fluxionality, electronic state fluctuation, and photochemically active characteristic in both solution and the solid state. Therefore, the organometallics which include the well-characterized organic photochromic moieties, considered to be derivatives of such kinds of organic photochromic compounds, are excluded in this article. Mono-, di-, and poly-nuclear organometallic compounds are presented based on the reaction types such as linkage isomerization, haptotropic rearrangement, and reorganization of metal–ligand and/or metal–metal bonds. Very recently, the crystalline-state photochromism is becoming an attractive field of photochromic chemistry. As a demonstrative example, the photochromism of organometallic rhodium dinuclear complexes having a dithionite ligand (μ-O₂SSO₂), which shows 100% reversible interconversion in the crystalline-state and have been developed in the authors’ laboratory, will be discussed.     

Photochromic hybrid organic-inorganic liquid-crystalline materials built from nonionic surfactants and polyoxometalates: elaboration and structural study

This work reports the elaboration and structural study of new hybrid organic-inorganic materials constructed via the coupling of liquid-crystalline nonionic surfactants and polyoxometalates (POMs). X-ray scattering and polarized light microscopy demonstrate that these hybrid materials, highly loaded with POMs (up to 18 wt %), are nanocomposites of liquid-crystalline lamellar structure (Lalpha), with viscoelastic properties close to those of gels. The interpretation of X-ray scattering data strongly suggests that the POMs are located close to the terminal -OH groups of the nonionic surfactants, within the aqueous sublayers. Moreover, these materials exhibit a reversible photochromism associated to the photoreduction of the polyanion. The photoinduced mixed-valence behavior has been characterized through ESR and UV-visible-near-IR spectroscopies that demonstrate the presence of W(V) metal cations and of the characteristic intervalence charge transfer band in the near-IR region, respectively. These hybrid nanocomposites exhibit optical properties that may be useful for applications involving UV-light-sensitive coatings or liquid-crystal-based photochromic switches. From a more fundamental point of view, these hybrid materials should be very helpful models for the study of both the static and dynamic properties of nano-objects confined within soft lamellar structures.