Reactivity of N-Phenylanthranilic Acid Derivatives: XIII. Electrical Conductivity of Solutions of Substituted 4-Nitro-N-phenylanthranilic Acids in the Dioxane-Water System

Conductometry was used to determine limiting equivalent electrical conductivity (₀), Pisarzhevskii-Valden product (₀₀), hydrodynamic ionic radii, ionization constants, thermodynamic parameters for substituted 4-nitro-N-phenylanthranilic acids (7 compounds) in the system dioxane-water at varioustemperatures. It was established that the ionization is endothermic and the entropy factor is prevailing. It was found that the reaction center is moderately sensitive to substituents and the sensitivity decreases with temperature. Multifactor correlation analysis showed that the reaction constants are roughly equal to r _I and _R but are half the values for substituted benzoic acids. The reaction series studied was found to be isoentropy. Inconsiderable solvation of the anions of the substituted anthranilic acids was revealed.     

强磁场作用对聚苯胺颗粒形貌及电性能的影响

聚苯胺的聚合掺杂条件对其颗粒结构及其导电性能有着很大的影响. 本文在10 T强磁场的作用下用化学氧化溶液原位聚合法得到聚苯胺并观察充分聚合后聚苯胺的颗粒结构、形貌特征及与其形成复合材料的电性能. 实验表明, 在没有强磁场作用下掺杂聚苯胺颗粒呈现礁石状, 而强磁场作用下的原位聚合聚苯胺颗粒呈现直径大约50 nm的棒状, 但其复合材料的电阻率与没有强磁场相比高出3个数量级; 本征态聚苯胺在强磁场下再掺杂得到20～30 nm的球状颗粒, 其复合材料电阻率却降低1个数量级. 分析认为这主要由于强磁场对聚苯胺晶粒的取向作用以及强磁场对聚合掺杂过程的影响所至.     

Comparative Theoretical Studies on Several Energetic Substituted Dioxin-imidazole Derivatives

The molecular structures, infrared spectra, heats of formation (HOFs), detonation properties, chemical and thermal stabilities of several tetrahydro-[1,4]dioxino[2,3-d:5,6-d'] diimidazole derivatives with different substituents were studied using DFT-B3LYP method. The properties of the compounds with different groups such as -NO₂, -NH₂, -N₃, and -ONO₂ were further compared. The -NO₂ and -ONO₂ groups are effective substituents for increasing the densities of the compounds, while the substitution of -N₃ group can produce the largest HOF. The compound with -NO₂ group has the same detonation properties as 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane, while the compound with -ONO₂ group has lower detonation properties than those of hexahydro-1,3,5-trinitro-1,3,5-triazine. The nature bond orbital analysis reveals that the relatively weak bonds in the molecules are the bonds between substituent groups and the molecular skeletons as well as C-O bonds in the dioxin rings. The electron withdrawing groups (-NO₂, -N₃, and -ONO₂) have inductive effects on the linkages between the groups and molecular skeletons. In addition, researches show that the electronegativities of the groups are related with the stabilities of the compounds. Considering detonation performance and thermal stability, the 1,5-dinitro-2,6-bis(trinitromethyl)-3a,4a,7a,8a-tetrahydro-[1,4]dioxino-[2,3-d:5,6-d'] diimidazole satisfies the requirements of high energy density materials.     

取代型钨镓杂多配合物的导电性及其磁性

合成了过渡金属取代的钨镓杂多配合物α－Ｎａ７「ＧａＷ１１Ｃｏ（Ｈ２Ｏ）Ｏ３９」．１６Ｈ２Ｏ，α－Ｎａ７Ｈ２「ＧａＷ１０Ｃｏ２（Ｈ２Ｏ）２Ｏ３９」．１６Ｈ２Ｏ和α－ＮａｎＨｍ「ＧａＷ９ＭＥ（Ｈ２Ｏ）３Ｏ３７」．１６Ｈ２Ｏ「Ｍ＝Ｃｏ（Ⅱ），Ｎｉ（Ⅱ，）Ｖ（Ⅴ）」，通过红外，紫外，ＩＣＰ，ＴＧ－ＤＴＡ，ＥＰＲ，ＸＰＳ，＾１８３ＷＮＭＲ，极谱等手段进行了表征。     

取代吡唑啉衍生物的合成与生物活性

采用α-三唑-β-烷氧基芳酮与肼关环,制备了1,3-二苯基-4-三唑基吡唑啉1a,1-苯基-3-对氯苯基-4-三唑基吡唑啉1b和3-取代苯基-4-三唑基吡唑啉(7),并研究了化合物7的成环优化条件.使用α,β-不饱和酮与肼关环合成了1,3,4,5-多取代吡唑啉衍生物1c-1h,并初步用质谱法确定了该反应产物的结构;同时,以3,5-二取代吡唑啉(6)和7作为中间体合成了1-,3-,4-或5-取代的化合物2a-2l.初步生物活性测定结果表明,所合成的化合物均有一定的杀菌、激素和除草效果.     

Pressure‐Induced Polymerization and Electrical Conductivity of a Polyiodide

We report the high‐pressure structural characterization of an organic polyiodide salt in which a progressive addition of iodine to triiodide groups occurs. Compression leads to the initial formation of discrete heptaiodide units, followed by polymerization to a 3D anionic network. Although the structural changes appear to be continuous, the insulating salt becomes a semiconducting polymer above 10 GPa. The features of the pre‐reactive state and the polymerized state are revealed by analysis of the computed electron and energy densities. The unusually high electrical conductivity can be explained with the formation of new bonds.     

聚苯胺电极的电导率

采用化学氧化聚合法制备聚苯胺(PANI)。利用四探针技术和电流-电压方法对PANI的电导率进行表征测试。基于电子-空穴导电机理和经典电流密度表达式,建立了PANI的有效导电数学模型,该模型可描述为电流密度、电压、温度的函数。对模型的图形分析表明,得到的电流-电压规律与PANI的实验结果一致。对电流密度与温度的关系分析得到的电导率随温度的变化规律与实验现象相符。结果表明:PANI有机半导体主要以耦合电流为主,电流强度随电压(温度)的增加呈现先增大后减小的趋势;低温时,PANI的导电性较好。     

Surface-Initiated Polymerization on Self-Assembled Monolayers: Effect of Reaction Conditions

Self-assembled monolayers of 4′-nitro-4-mercaptobiphenyl were modified by electron beam irradiation and diazotization to create a surface-bond asymmetric azo initiator for the surface-initiated polymerization (SIP). The effect of different reaction conditions upon the thermally and photochemical initiated SIP was investigated.     

新型萘/苝酰亚胺取代丁二炔衍生物的合成及拓扑聚合

经5步反应制备了萘/苝酰亚胺取代的端炔和碘炔单体, 通过Sonagashira偶联反应合成了2个新型对称丁二炔单体浅黄色粉末2-[4-(4-{4-[7-(庚-3-基)-1,3,6,8-四氧亚基-1,2,3,6,7,8-六氢异喹啉并[6,5,4-def]异喹啉-2-基]苯基}丁-1,3-二炔基)苯基]-7-(辛-4-基)-1,2,3,6,7,8-六氢异喹啉并[6,5,4-def]异喹啉-1,3,6,8-四酮(diNDI)和暗红色粉末2-[4-(4-{4-[1,3,8,10-四氧亚基-9-(二十三烷-12-基)-1,2,3,8,9,10-六氢异喹啉并[6',5',4':9,1,2]蒽并[6,5,10-def]异喹啉-2-基]苯基}丁-1,3-二炔基)苯基]-9-(二十三烷-12-基)-1,2,3,8,9,10-六氢异喹啉并[6',5',4':9,1,2]蒽并 [6,5,10-def]异喹啉-1,3,8,10-四酮(diPDI), 产率分别达60%和70%. 由于NDI和PDI基元的强吸电子作用, diNDI和diPDI表现较低的最低未占分子轨道(LUMO)能级, 分别为?3.80和?3.70 eV. 单晶数据表明, 萘酰亚胺基元的分子间氢键及π-π作用对diNDI分子堆积结构起主导作用, diNDI呈层状堆积模式. 由差示扫描量热(DSC)实验结果可知, diNDI丁二炔经加热可发生固态聚合. 加热条件下diNDI的紫外-可见吸收光谱及原位拉曼光谱特征峰以及在波长532 nm激光强度为10%的辐照条件下原位拉曼光谱特征峰的变化均表明diNDI微纳晶发生了非常规的1,4-加成聚合, 并且新生成的共轭主链是无序的, 同时发现激光辐照条件下更易促进聚合反应.     

偶氮苯取代吡唑啉衍生物的制备及其电子光谱研究

含有多个生色团化合物的内部较易实现分子内的能量传递、电子转移或电荷分离 ,因此 ,设计制备具有新颖结构的多功能化合物不仅在分子电子学和分子光子学等领域备受关注 ,同时也是模拟研究生物体内生命过程的重要内容 .由于吡唑啉具有较高的荧光量子产率和较好的空穴传输特性 ,在电致发光器件中已有广泛的研究 [1～ 3] ,同时偶氮苯类化合物的光致顺反异构化性质及其在异构化过程中伴随的结构、偶极矩及光学性质的改变 ,使其在光学信息存储、光化学开关和非线性光学等领域中具有极其广阔的应用前景 [4～ 7] .本文设计合成了通过柔性链将偶氮苯…     

Electrical Conductivity of an Individual Polyaniline Nanotube Synthesized by a Self‐Assembly Method

Camphor sulfonic acid (CSA) doped polyaniline (PANI) nanotubes (175 nm in outer diameter and 120 nm in inner diameter) were synthesized successfully by a self‐assembly method. It is found that the room‐temperature conductivity of an individual PANI nanotube is 30.5 S · cm⁻¹; in particular, the intrinsic resistance of an individual nanotube (30 kΩ) is much smaller than the contact resistance of crossed nanotubes (500 kΩ).

A SEM image of two crossed PANI‐CSA nanotubes and the attached Pt electrodes.     

聚合介质酸度对聚苯胺的结构和性能的影响

不论电化学还是化学聚合,酸度对聚苯胺(PAn)的合成都有很大影响,说明只有在酸性条件下才能合成电活性的聚苯胺,鉴于聚合介质的酸度对聚苯胺的影响尚无详细的报道,本文研究了聚合介质酸度对聚苯胺的结构和性能的影响.     

吖啶酮类衍生物的光电性质研究

测定了8个吖啶酮类衍生物的紫外吸收光谱、荧光光谱和荧光量子产率,以研究它们的结构与光学性质之间的关系,用循环伏安法测出它们各自的电子势．发现吖啶酮类衍生物都具有较高的电子亲和势,表现出比常用的电子传输材料2-(4-联苯基)-5-(叔丁苯基1—1,3,4-二唑(PBD)更容易被还原的优良电化学性能。     

Studies with Alkylheterocycles: Novel Synthesis of Functionally Substituted Isoquinoline and Pyridopyridines Derivatives

Several isoquinolines were prepared via reacting pyridine 4 with cinnamonitriles 5a‐c or 5d‐f . Treating 4 with elemental sulphur yielded thienopyridine 9. 9 reacts with acrylonitrile to give isoquinoline 12. 12 was also prepared from 4 and methylenemalononitrile. Condensation of 4 with aromatic aldehydes gave the arylidine 13. 13 afforded the pyridine 14 and 15 on treating it with NH₄OH and AcOH/HCl, respectively.     

Study on Nanofibers of Polyaniline via Interfacial Polymerization

Uniform polyaniline nanofibers were prepared by interfacial polymerization. The nanofibers had a diameter of 80 nm and a length of about 1μm. The effect of centrifugal force on the morphology of the nanofibers is discussed. In situ UV‐Vis spectra indicated that the interfacial polymerization process was similar to the solution polymerization process. An “expanded‐partly doped” stage of interfacial polymerization was observed for the first time in the in situ UV‐Vis spectra.     

Kinetic Studies on SNAr Reactions of Substituted Benzofurazan Derivatives: Quantification of the Electrophilic Reactivities and Effect of Amine Nature on Reaction Mechanism

Kinetics of the nucleophilic aromatic substitution reactions of 7‐L‐4‐nitrobenzofurazans 1 ( 1a : L = Cl and 1b : L = OCH₃) and secondary cyclic amines (morpholine, piperidine, and pyrolidine) 2a–c have been measured in acetonitrile solution at 20°C. The derived values of second‐order rate constants (k ₁) have been employed to determine the electrophilicity parameters E for both benzofurazans 1a and 1b according to the linear free enthalpy relationship: log k (20°C) = s_N(E + N ) (Eq. 1 ). The second‐order rate constants for reactions of benzofurazans 1 with a series of 4‐X‐substituted anilines 3a–d (X = OH, OCH₃, CH₃, and H) have also been measured in MeCN and found to agree within a factor of 0.14–50 with those calculated by Eq. 1 from the electrophilicity parameters E measured in this work and the known nucleophile‐specific parameters N and s _N of anilines 3 . On the other hand, the reactions of these benzofurazans 1 with anilines 3 exhibit linear Brønsted‐type plots with β_nuc = 1.27 for 1a and 1.01 for 1b , which are considerably greater than those (0.57 for 1a and 0.62 for 1b ) obtained with the secondary cyclic amines 2 . These high values of β_nuc have been interpreted in terms of a single electron transfer mechanism. Secondary evidence for the validity of this mechanism is provided by the agreement between the rate constants, k ₁, for substitution of benzofurazans 1 by the anilines 3 and their oxidation potentials E °.     

Enhanced Conductivity of Polyaniline by Conjugated Crosslinking

A novel crosslinked conductive polyaniline (PANI) was prepared by chemically copolymerizing aniline (An) and p‐phenylenediamine (PPDA) with triphenylamine (TPA) as crosslinker, using ammonium peroxydisulfate (APS) as an oxidant. The effects of different preparation conditions on the electrical conductivity of polymers were systematically investigated by adjusting acid kinds, concentration, the ratio of APS/An, the mounts of TPA and PPDA. The crosslinked PANI displayed a conductivity increase of up to 25% compared with the linear one. Their structures were characterized by Fourier‐transformed infrared spectroscopy and X‐ray photoelectron spectroscopy, and the electrical conductivity was also tested by a typical four‐point probe (RTS‐8) technique.

     

Triazole‐Substituted Nitroarene Derivatives: Synthesis,Characterization, and Energetic Studies

A series of dense and energetic polynitroaryl‐1,2,4‐triazoles were synthesized through the nitration of aryl‐1,2,4‐triazoles. The Cu‐catalyzed/base‐mediated coupling reactions of haloarenes with 1,2,4‐triazoles delivered N‐aryl‐1,2,4‐triazoles. These new nitro‐rich‐aryltriazoles were characterized by analytical and spectroscopic methods. The solid‐state structures of most of these compounds were established by X‐ray diffraction analysis. Their thermal properties were determined by differential scanning calorimetry–thermogravimetric analysis. Their heats of formation (HOFs) and crystal densities were also calculated. The densities of the synthesized compounds ranged from 1.40 to 1.85 g cm^?3. Some of these newly synthesized compounds exhibited high positive HOFs, good thermal stabilities, high densities, and reasonable detonation velocities and pressures.