过渡金属一取代Keggin结构钼磷酸盐掺杂的聚吡咯的制备、表征与导电性研究

０引言有机高分子－多酸导电聚合物是８０年代末兴起的一类新型有机－无机杂化材料。由于它兼有无机组分和有机聚合物基块的性能，并能衍生出新的导电性、光学性、耐摩擦、力学性能、功能梯度等，它现已成为材料科学和化学科学研究的前沿课题之一犤１犦。多酸是一类含有氧桥的多核配合物，具有强酸性、强氧化性、优良的催化活性、光致变色、电致变色性及高质子导电性等，可作为构建有机－无机杂化材料的基块犤２，３犦。聚吡咯是一类有机高分子，其合成简便、空气稳定性好、易于掺杂，通过掺杂可形成高电导率的高分子材料。若将多酸掺杂聚吡…     

不同质子酸掺杂对银/聚苯胺纳米复合材料结构和导电性的影响

利用紫外光作为辅助条件,在反胶束体系中采用一步双原位法合成了硝酸(HNO3)、对甲基苯磺酸(TSA)和5-磺基水杨酸(SSA)掺杂的银/聚苯胺(Ag/PANI)纳米复合材料.通过对复合材料进行红外光谱(FTIR)、紫外光谱(UV-Vis)、扫描电镜(SEM)、X射线衍射(XRD)和导电性能的测试,研究了不同质子酸对Ag/PANI纳米复合材料结构、形貌和导电性能的影响.测试结果表明,3种酸掺杂制备的Ag/PANI纳米复合材料均为聚苯胺包覆银粒子的核-壳结构.不同的质子酸掺杂会对Ag/PANI纳米复合材料的电性能有重要影响.在3种酸掺杂的复合材料中,TSA掺杂的复合材料的电导率最佳,为215.14 S·cm-1.     

氢键诱导聚马来酸单酯液晶复合物的合成及表征

合成了聚马来酸６－（４－辛氧基偶氮苯氧基）－１－己酯（ＰＭＡＮ－ＯＡＢ），并以其为质子给体，４－（４－庚氧基苯甲酰氧基）－苯乙烯基吡啶（７ＳＺ）为质子受体，研究了两者复合前后的液晶行为，结果表明，ＰＭＡＮ－ＯＡＢ在液晶态时是以羧酸二聚体形式存在的，其倾角为３９．３°，７ＳＺ含量在４０％～９０％范围内的复合物液晶范围比７ＳＺ和ＰＭＡＮ－ＯＡＢ的宽。     

多酸插层水滑石复合材料的新进展

层状双金属氢氧化物是一类重要的阴离子层状材料,通过调变层间阴离子的种类和数量,可以得到性能丰富的复合材料.多金属氧酸盐(简称多酸)是一类结构明确、种类多样、性能丰富的阴离子材料.将多酸插入阴离子层状材料中,可以实现电荷平衡以及尺寸匹配,并且主体和客体之间的多重相互作用有助于多酸的分散和稳定.这类多酸插层水滑石复合材料在环境、能源、催化等领域具有重要的应用.本文综述了近年来多酸插层水滑石材料的制备方法及其在不同应用领域的最新进展.     

有机阳离子-无机多阴离子复合物:高分子体系中的组装及其自组装

有机阳离子包覆多金属氧簇无机多阴离子形成的具有确定化学组成、两亲性核壳结构超分子复合物,具有易于调控和集成有机和无机组分结构与功能的特性.以此类复合物为预组装体的自组装和高分子功能杂化材料展现了一类具有多方面构筑超分子组装体的新型构筑基元体系.如何实现预组装体复合物在结构稳定、具有良好加工性基材中的组装和功能化成为这一领域的重要研究内容.本文系统地总结了基于此类超分子复合物的高分子纳米复合材料和溶液中组装方面的研究进展与发展趋势.     

掺杂质子酸的类型对聚苯胺结构和电导率的影响

采用化学氧化聚合法以苯胺为单体，过硫酸铵为氧化剂，在不同质子酸的水溶液中合成聚苯胺，考察质子酸对聚苯胺电性能影响，并通过傅立叶红外吸收光谱（FTIR）和紫外可见光吸收光谱（UV－vis)研究聚苯胺掺杂前后结构的变化。结果表明，龙质子酸掺杂后聚 胺具有导电性是因为其分子链上电荷离城形成了共轭结构，具有不同质子酸中生成的聚苯胺氧化程度不同；分子链共轭程度与掺杂酸对阴离子大小有关，掺杂质子酸对阴离子越大，聚苯胺分子链共轭程度越大，电导率也就越高。     

α－蒎烯选择性二聚合及低聚反应研究 Ⅰ．不同催化剂体系的聚合行为和产物构成

从聚合动力学、异构化和产物构成等方面检讨了质子酸、Ｌｅｗｉｓ酸和质子酸／Ｌｅｗｉｓ酸复合酸三类，多种催化剂和各种反应条件对α－蒎烯的二聚合及低聚反应的影响，结果表明，活性种为质子Ｈ＾＋的这三类催化剂主要生成二、三、四聚体产物，发现质子酸与Ｌｅｉｗｓ酸组成的复合催化剂比单独时聚合活性大幅度提高，异构化作用显著减少，可以高选择性地合成二聚体，如复合催化剂ＡｌＣｌ３／ＣＦ３ＣＯＯＨ异构化率仅０．５％；聚     

Keggin结构钨磷酸/聚乙烯吡咯烷酮复合膜的制备和光致变色性质研究

近年来,由于无机－有机复合材料具有潜在的应用前景和特殊性能,尤其是光致变色性能,引起研究者们的广泛兴趣^[1-3],以杂多化合物为多核配合物,通过化合键或氢键作用与高分子底物结合,形成电荷转移物质,可以大大提高复合材料的化学和物理性能。目前,这一领域的研究在国外已经成为热点^[4-7]。本文以Keggin结构钨磷酸和聚乙烯吡咯烷酮为原料,报道了该类复合物的合成、表征及光致变色性质。     

氢键诱导聚马来酸单酸液晶复合物的合成及表征

合成了聚马来酸６－（４－辛氧基偶氮苯氧基）在－己酯，并以其为质子给体，４－（４－庚氧基苯甲酰氧基）－苯乙烯基吡啶为质子受体，研究了两者复合前后的液晶行为。     

一系列氢键诱导液晶复合物的合成及表征

以２－氰基－３－（４－（２－氯－３－甲基－１－丁酰氧基）－苯基丙烯酸（Ａ）为质子给体，Ｎ－（４－吡啶基亚甲基）－４－烷氧基苯胺（ｎＳＳＺ）为质子受体，合成了一系列新的氢键复和物，经红外光谱证实了分子间氢键的存在，通过ＤＳＣ，偏光方法及Ｘ射线衍射方法对其液晶行为进行研究，结果表明复合物呈现近晶相行为。     

Synthesis and Spectroscopic Characterization of a Complex of 1, 10‐Phenanthroline with Magnesium

The complex [Mg(1, 10‐phenanthroline)₃(NO₃)₂]·9H₂O has been synthesized. It forms crystals having the shape of sheaves with very thin filaments. The compound has been characterized by UV, IR, NMR and mass spectra. The UV and mass spectra are indicative of an electron density transfer from NO₃^— to Mg²⁺. On the base of the spectroscopic studies a model of the crystal structure has been proposed.     

Effect of gamma radiation on folic acid and its cobalt complex solutions

Gamma-radiolysis of folic acid and its cobalt complex were studied in aqueous solutions at doses ranged from 2 to 10 krad and from 2 to 10 Mrad using⁶⁰Co source. The variations in their spectra of IR, UV, and visible due to their radiolysis were shown. Also the change in pH after radiolysis was determined. The results showed that decomposition of folic acid by gamma-radiation occurred without variation of pH. Fine measurements of pH for irradiated CoCl₂ and cobalt-folic acid complex solutions can be utilized for dose determination in the studied range of 2–10 Mrad. IR spectra showed that addition of cobalt chloride to folic acid decreased its decomposition by gamma-radiation. This result proved the importance of addition of cobalt chloride in keeping foodstuffs, which contain folic acid, by irradiation. The mechanism for the effect of radiation on cobalt chloride and cobalt-folic acid complex was discussed.     

Über die Tribromomangan(II)-Säure und deren Komplex mit Pyridin

Tribromomanganese(II) acid has been prepared for the first time and will be described. A complex of the acid with pyridine was obtained and its UV, visible, IR and¹H-NMR spectra will be reported.     

Ionization‐Induced Solvent Migration in Acetanilide‐Methanol Clusters Inferred from Isomer‐Selective Infrared Spectroscopy

We present the resonance‐enhanced multiphoton ionization, infrared‐ultraviolet hole burning (IR‐UV HB), and IR dip spectra of the trans‐acetanilide–methanol (AA–MeOH) cluster in the S₀, S₁, and cationic ground state (D₀) in a supersonic jet. The IR‐UV HB spectra demonstrate the co‐existence of two isomers in S_0,1, in which MeOH binds either to the NH or the CO site of the peptide linkage in AA, denoted as AA(NH)–MeOH and AA(CO)–MeOH. When AA(CO)–MeOH is selectively ionized, its IR spectrum in D₀ is the same as that measured for AA⁺(NH)–MeOH. Thus, photoionization of AA(CO)–MeOH induces migration of MeOH from the CO to the NH site with 100% yield.     

IR and Raman spectroscopic study of the photopolymerization of Langmuir-Blodgett films of acetylenic acids

The UV induced photopolymerization of Langmuir-Blodgett films of lead salt of 2-docosynoic acid (CH₃(CH₂)₁₈C=CCOOH) is studied using IR and Raman spectroscopy. It is found that the films are a highly ordered system with trans-configuration of alkyl chains and a bridged complex generated between the carboxyl group and the lead ion. Based on a change in the absorption band intensity in the IR spectra corresponding to the triple bond vibration, the degree of polymerization depending on the irradiation time is determined. In the Raman spectra, a peak at ∼1635 cm⁻¹ appears during polymerization, which corresponds to the C=C double bond. The formation of conjugated double bonds in these systems is observed for the first time. During polymerization, methylene chains of molecules retain trans-configuration; the structural ordering of molecules in the film is observed.     

A complex between ammonia and chlorine studied at 20°K in a nitrogen matrix

UV and IR spectra of ammonia and chlorine codeposited in a nitrogen matrix at 20°K have been recorded. An intense absorption band round 2500 Å has been observed. An IR-active chlorine stretch frequency of about 460 cm^?1 and small shifts on the ammonia absorptions were determined. The results are discussed in terms of a charge transfer complex between ammonia and chlorine. From the complex shifts for ammonia and ammonia-d₃ an opening up of the HNH bond angle on complexing by about 3.6° has been calculated.     

Homoleptic Zinc(II) Complexes Based on 4′‐(2‐Thienyl)‐terpyridine: Preparation,Structures, and Properties

The homoleptic complexes Zn^II(4′‐(2‐(5‐R‐thienyl))‐terpyridine)₂(ClO₄)₂ [R = hydrogen ( 1 ), bromo ( 2 ), methyl ( 3 ), and methoxy ( 4 )] were prepared. Their structures were determined by single‐crystal X‐ray diffraction analyses, and further characterized by high resolution mass, infrared spectra (IR), and elemental analyses. Single crystal X‐ray diffraction analysis showed that Zn^II ions in the complexes are both six‐coordinate with N₆ coordination sphere, displaying distorted octahedral arrangements. The absorption and emission spectra of the homoleptic Zn^II complexes were investigated and compared to those of the parent complex Zn^II(4′‐(2‐thienyl))‐terpyridine)₂(ClO₄)₂. The UV/Vis absorption spectra showed that the complexes all exhibit strong absorption component in UV region, moreover, complex 4 has an absorption component in the visible region. Thus, the photocatalytic activities of the complexes in degradation of organic dyes were investigated under UV and visible irradiation.     

Synthesis, spectral studies, crystal structures and TDDFT studies of the rhenium(I) complexes of 2,4-dihydroxy-N′-(4-hydroxybenzilidene) benzohydrazide

The rhenium(I) carbonyl bromide complex, [ReBr(CO)₃(HL)], of the ligand derived from 2,4-dihydroxybenzaldehyde and 4-hydroxybenzoic acid hydrazide (HL), has been prepared. HL and its complex have been characterized by elemental analysis, MS, IR, UV-Vis and ¹H NMR spectroscopic methods. The structure of HL and the aqua-complex [Re(OH₂)(CO)₃(L)] where the ligands are monodeprotonated have been elucidated by X-ray diffraction. The structure of [ReBr(CO)₃(HL)] has been calculated from conformational parameters found in the aqua-complex. DFT and TDDFT calculations have been performed to obtain the IR spectra and UV-Vis absorption and emission spectra. The calculated spectra agree with the experimental results.     

具有分子内折叠结构锌配合物的合成，与DNA键合及其对DNA切割作用研究

本文报道了一个锌配合物[Zn(bipy)(pmal)(H2O)]·2H2O（其中bipy = 2,2’-联吡啶, pmal = 苯基丙二酸）的合成,晶体结构及其光谱学研究。并通过单晶X射线衍射,元素分析,红外光谱等手段对它进行了表征。同时,利用紫外光谱和荧光光谱方法考察了该配合物与小牛胸腺DNA的键和作用。琼脂糖凝胶电泳实验的结果说明该配合物的平面结构对pBR 322DNA切割作用显著。     

Does the proton-transfer reaction take place in the ground state of phenol?(H2O)4 clusters?

In recent experimental studies of infrared (IR) spectra of hydrated phenol clusters, the Mikami and Ebata group at Tohoku University attributed apparently two very different spectra to PhOH(H₂O)₄. The first spectrum has a wide transparent region between 3500 and 3700 cm^-1, which they named a window region. The second spectrum has several absorption bands in this window region. Our previous study revealed that the first spectrum was assigned to the isomers which have a single-ring structure of a hydrogen-bonding network of OH's of phenol and waters. The experimentalists suggested that the second spectrum might be identified to a proton-transferred phenol(SINGLEBOND)water cluster. In the present article, the geometrical structures of proton-transferred hydrated phenol clusters were determined with the ab initio molecular orbital method and their IR spectra were calculated. The proton-transferred phenol(SINGLEBOND)water cluster is at a stable local minimum, but the energy is much higher than that of the most stable nontransferred cluster. The calculated IR spectrum has a still wider window region and is far different from the experimental spectrum of the second type. © 1996 John Wiley & Sons, Inc.