n-型掺杂反式聚乙炔导电性能各向异性研究

根据固体能带理论，用量子化学ＥＨＭＯ／ ＣＯ 方法，计算了高取向反式聚乙炔及其ｎ－ 型掺杂态（掺杂Ｌｉ，Ｎａ，Ｋ） 的二维能带结构，首次从能隙与带宽角度讨论了聚乙炔经ｎ－ 型掺杂呈现的导电性能的各向异性．研究表明：平行和垂直于分子链方向的电导率之比（σ∥／σ⊥） 取决于这两个方向上能隙和带宽的大小；掺杂后σ∥／σ⊥下降，其原因是掺杂剂在聚乙炔链间架起了一个“浮桥”，使链间耦合作用增强．理论计算与实验结果一致     

碘掺杂和非掺杂高取向反式聚乙炔导电性能的各向异性

本文应用量子化学EHMO/CO方法计算了高取向反式聚乙炔及其碘掺杂物的二维能带结构,并以此为依据讨论了它们导电性能的各向异性.平行于分子链方向的电导率与垂直于该方向的电导率之比(σ_■,/σ_⊥)取决于这两个方向上价带宽和导带宽的大小.碘掺杂后σ_■/σ_⊥下降,其原因是链间耦合增强的结果.这也使掺杂后的反式聚乙炔成为链间相互作用微弱的三维体系.计算结果与实验结果较好地吻合.     

磺掺杂和非掺杂高取向反式聚乙炔导电性能的各向异性

本文应用量子化学EHMO/CO方法计算了高取向反式聚乙炔及其碘掺杂物的二维能带结构,并以此为依据讨论了它们导电性能的各向异性.平行于分子链方向的电导率与垂直于该方向的电导率之比(σ~1/σ~⊥)取决于这两个方向上价带宽和导带宽的大小.碘掺杂后σ~1/σ~⊥下降,其原因是链间耦合增强的结果.这也使掺杂后的反式聚乙炔成为链间相互作用微弱的三维体系.计算结果与实验结果较好地吻合.     

磺掺杂和非掺杂高取向反式聚乙炔导电性能的各向异性

本文应用量子化学EHMO/CO方法计算了高取向反式聚乙炔及其碘掺杂物的二维能带结构,并以此为依据讨论了它们导电性能的各向异性.平行于分子链方向的电导率与垂直于该方向的电导率之比(σ~1/σ~⊥)取决于这两个方向上价带宽和导带宽的大小.碘掺杂后σ~1/σ~⊥下降,其原因是链间耦合增强的结果.这也使掺杂后的反式聚乙炔成为链间相互作用微弱的三维体系.计算结果与实验结果较好地吻合.     

溴和碘掺杂高取向反式聚乙炔导电性能各向异性研究

根据固体能带理论,用EHMO/CO方法,计算了高取向反式聚乙炔及溴和碘掺杂态的二维能带结构,讨论了其导电性能的各向异性.研究表明,平行和垂直于分子链方向的电导率之比(σ_///σ_⊥上)取决于这两个方向上能隙和带宽的大小掺杂后σ_///σ_⊥下降是由于掺杂剂使链间栖合作用增强所致.理论计算与实验结果一致.     

聚乙炔掺杂导电的双向机制

提出了一种掺杂聚乙炔的双向导电机理。垂直聚乙炔分子链方向的电荷输运是通过掺杂原子(或分子)在链间振动实现的;平行分子链方向的电荷输运是通过电荷密度波的传播实现的。掺杂聚乙炔的电导率随掺杂剂与聚乙炔链之间电荷转移量的增大而增大。     

电解聚合法合成导电高分子

一、引言有机化合物的电子受σ轨道束缚不能移动,有机物晶体多为分子晶体,分子间的作用力非常小,所以有机化合物是众所周知的绝缘体.要使有机高分子赋于导电性,必须设想种种途径,用低的能量就能产生大量载流子,并使载流子有很好的流动性.对高分子来说,使π轨道重叠,产生π共轭和加强分子之间的作用是导电高分子的结构条件.聚乙炔作为具有最简单共轭双键的导电高分子首先受到人们的注意.自1977年发现掺杂后聚乙炔具有接近金属的导电能力后,出现了研究导电高分子的新浪潮.人们以对聚乙炔的研究为开端,逐步拓展     

稀土聚乙炔的ESR研究

本文系统地研究了稀土聚乙炔的电子自旋共振(ESR)行为。发现稀土聚乙炔的ESR谱都为单线谱,符合Lorentz线型;十五种稀土环烷酸盐体系聚乙炔的ESR无明显区别,g因子为2.0028±0.0001;线宽(△H)和logN(N为未成对电子浓度)与聚乙炔的顺式含量成直线关系;未成对电子的形成服从零级动力学,其活化能为11.3kcal/mol;微量碘掺杂聚乙炔的ESR仍为单线谱、Lorentz型及g因子不变,碘掺杂浓度大于～2mol％时,没有ESR信号。     

聚苯胺/顺丁橡胶复合导电膜的制备与性能(Ⅱ)

采用再掺杂方法制得了樟脑磺酸掺杂的聚苯胺(PAn-CSA),用溶液共混法制备PAn／BR导电复合膜．研究了聚苯胺与顺丁橡胶(BR)复合膜在间甲酚二次掺杂前后电导率的变化。实验表明:CSA对聚苯胺有较好的掺杂作用;二次掺杂使PAn复合膜电导率明显提高,其导电渗滤阈值略有降低,使卷曲的二次掺杂PAn链展开并通过分子链间的相互作用而自行组成导电通路．     

共轭聚全氟丁炔-2的合成和性质

<正> 由于聚乙炔具有导电性能,近年来,人们对聚炔烃化学引起了广泛的重视。1979年Yamabe等设想用氟原子取代聚乙炔上的氢原子,期望得到对氧稳定的聚炔烃。最近Bubner等报道了用正丁基锂和氯化钯在DMF中催化三氟申基乙炔得到稳定的低分子量线型聚合物。当用碘蒸气掺杂后,其电导率σ_(max)达9.510~(-5)~(-1)cm~(-1)。另有文献报道     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.