聚苯基（聚苄基）甲基硅氧烷的氟烷基化反应研究

通过苯基甲基二乙氧基硅烷和苄基甲基二乙氧基硅烷的缩合反应制备了聚苯基甲基和聚苄基甲基硅氧烷。研究了它们与含氟酰基过氧化物间的反应。经酸碱滴定及ＩＲ、＾１Ｈ ＮＭＲ和＾１９Ｆ ＮＭＲ光谱分析确证反应主要生成苯环上氟烷基取代产物。通过测定经氟烷基化后聚硅氧烷处理的玻璃表面的接触角，初步评价了氟烷基化率对其表现性能变化的影响。     

基于三联吡啶/苯三羧酸类配体构筑的两个配合物的合成、结构和性质（英文）

基于H_3tbtd、H_3bbta和bpy配体在水热条件下合成了配位聚合物{[Co_3(tbtd)_2(bpy)_2(H_2O)]·5H_2O}_(n )(1)和配合物[Cd_2(Hbbta)(bpy)_3(C_2O_4)(H_2O)](2)(H_3tbtd=4-(2,4,6-三羧基苯基)-2,2′,6′,2″-三联吡啶,H_3bbta=1-氟-2,4,6-苯三酸,bpy=2,2′-联吡啶),并用元素分析、红外光谱、X射线单晶衍射等对其进行了表征。配聚物1为二维网状结构,基于丰富的氢键作用扩展形成三维超分子网结构。配合物2为双核结构,相邻的双核结构通过吡啶环之间的π…π堆积作用和氢键作用扩展为二维超分子网状结构。配聚物1在紫外光照射下对染料甲基橙(MO)的降解具有光催化活性,对紫外光催化具有良好的稳定性。此外还研究了配合物2的荧光性质和配合物1～2的热稳定性。     

三氟甲基取代Ir配合物的电子结构和磷光性质的理论研究

采用密度泛函理论m PW1PW91方法研究了三氟甲基(CF3)基团修饰的一类Ir磷光材料,即Ir(C∧C)(ppy)2、Ir(C∧C)(ppy)(Ort CF3)、Ir(C∧C)(ppy)(Me CF3)和Ir(C∧C)(ppy)(Par CF3)[(C∧C:3-甲基-1-(2,4-甲基苯)-1H-咪唑;ppy:2-苯基吡啶,Ort CF3=2-(2-(三氟甲基)苯基)吡啶;Me CF3:2-(3-(三氟甲基)苯基)吡啶;Par CF3:2-(4-(三氟甲基)苯基)吡啶]的电子结构和光学性质.理论计算得到Ir(C∧C)(ppy)2的电子结构、吸收光谱和磷光光谱与实验结果吻合得较好.通过与实验分子Ir(C∧C)(ppy)2对比,向ppy的邻位和对位引入CF3基团加强金属和配体之间的作用力,提高空穴和电子注入能力,吸收和磷光发射光谱发生红移.尤其,Ir(C∧C)(ppy)-(Ort CF3)比其他配合物在发射磷光时金属到配体的电荷转移(3MLCT)的贡献大、跃迁偶极矩(μS1)大、d轨道能级分裂大,并且单三重态分裂能(ΔES1-T1)小,这表明设计的分子Ir(C∧C)(ppy)(Ort CF3)有望成为好的磷光发光材料.     

基于三联吡啶/苯三羧酸类配体构筑的两个配合物的合成、结构和性质

基于H3tbtd、H3bbta和bpy配体在水热条件下合成了配位聚合物{[Co3(tbtd)2(bpy)2(H2O)]·5H2O}n(1)和配合物[Cd2(Hbbta)(bpy)3(C2O4)(H2O)](2)(H3tbtd=4?(2,4,6?三羧基苯基)?2,2′,6′,2″?三联吡啶,H3bbta=1?氟?2,4,6?苯三酸,bpy=2,2′?联吡啶),并用元素分析、红外光谱、X射线单晶衍射等对其进行了表征。配聚物1为二维网状结构,基于丰富的氢键作用扩展形成三维超分子网结构。配合物2为双核结构,相邻的双核结构通过吡啶环之间的π…π堆积作用和氢键作用扩展为二维超分子网状结构。配聚物1在紫外光照射下对染料甲基橙(MO)的降解具有光催化活性,对紫外光催化具有良好的稳定性。此外还研究了配合物2的荧光性质和配合物1~2的热稳定性。     

液体聚硅烷的合成与交联

采用具有不同有机取代基的二氯硅烷与甲基二苯基氯硅烷为原料,在甲苯中以金属钠共缩合的方法,合成了可流动的聚硅烷。这些聚硅烷可用灌注、浇铸、涂敷等方法制成各种形状,并能在多乙烯基硅烷存在下,以紫外光辐照进行交联。本文还讨论了这些聚硅烷的分子量分布以及红外、紫外、核磁共振等光谱性质。     

超支化聚(酰胺-酯)的端基光致变色改性研究

采用丁二酸酐、三羟甲基氨基甲烷为主要原料,先在冰水浴条件下合成AB3型单体,然后进行熔融缩聚制得超支化聚(酰胺-酯)(HBP),最后用4-(4′-二甲氨基苯基偶氮)苯甲酸对HBP的末端羟基进行功能化改性,得到了一种具有光致变色和酸碱变色性的HBP;用紫外光谱对改性超支化聚(酰胺-酯)的变色性进行了研究。结果表明：随紫外光照时间延长紫外吸收强度增加;随pH值增大紫外吸收波长向短波方向移动。     

Synthesis of Si—H Functional Poly(phenylsilane) and Organosilane Copolymers: Low-valent Titanium Induced Polymerization of Organodichlorosilanes

在低价钛促进下,苯基二氯硅烷进行还原聚合反应生成Si-H官能化的聚苯基硅烷。应用此方法,在温和、中性反应条件下制备出Si-H官能团化的有机聚硅烷共聚物。     

3-芳基香豆素衍生物的合成及其生物活性研究

对3-芳基香豆素母核进行修饰，以芳基乙酸和水杨醛为起始原料，三乙胺为催化剂，乙酸酐为溶剂，经缩合反应分别引入吸电子基团三氟甲基和给电子基甲氧基，合成了3-(4′-三氟甲基苯基)香豆素（2a）和新化合物3-(4′-甲氧基苯基)香豆素（2b），其结构经UV-Vis、 ¹H NMR、 IR和MS表征。并对其生物活性和荧光标记特性进行了研究。结果表明：2a和2b显示较强的细胞增殖抑制活性、抑菌活性，浓度为4000 μmol·L^-1时，对ECV304细胞的抑制率分别为84.22%和65.56%，对大肠杆菌、绿脓杆菌和金黄色葡萄球菌均显示抑菌活性，具有较好的荧光特性，可用于细胞染色及荧光标记。     

N-(4-氯-3-三氟甲基苯基)-N′-(对取代苯基)脲的合成

以4-氯-3-三氟甲基苯胺、固体光气、对取代苯胺为原料,采用一锅法合成了N-(4-氯-3-三氟甲基苯基)-N-′(对甲基苯基)脲和N-(4-氯-3-三氟甲基苯基)-N-′(对溴苯基)脲,其结构经1H NMR,IR和元素分析表征。     

含功能性季铵盐三苯胺聚合物的合成与电致变色和非易失性记忆性能

通过4-(4-氨基苯氧基)吡啶与4,4'-二溴二苯醚或1,4-二溴苯的偶合反应(Buchwald-Hartwig),得到聚[(4-(吡啶-4-氧基)-p-苯氧基]三苯胺或聚[4-(吡啶-4-氧基)]三苯胺,再与3-(氯甲基)-5-[4-(三氟甲基)苯基]-1,2,4-噁二唑进行季铵化反应,得到含功能性季铵盐三苯胺聚合物:聚[N-对苯氧基-N-[4-O-[2-对三氟甲基苯基-(4-氯化吡啶盐)噁二唑]基]三苯胺(PTP3FQ)和聚[N-[4-O-[2-对三氟甲基苯基-(4-氯化吡啶盐)噁二唑]基]三苯胺(PP3FQ).用核磁氢谱和红外光谱表征了PTP3FQ和PP3FQ的结构,用热失重和循环伏安法测定了PTP3FQ和PP3FQ的热性能和电化学性能.结果表明,在不外加电解质情况下,PTP3FQ和PP3FQ利用自身的季铵盐离子表现出良好的电致变色性能;将PTP3FQ和PP3FQ制成Al/聚合物/ITO结构的记忆器件,由于噁二唑基团与三苯胺形成电荷转移络合物,使记忆器件表现出非易失性可擦写(Flash)存储特性,开关比高达10~3.     

羧酸衍生物取代甲基苯基聚硅烷制备杂取代聚硅烷

以甲基苯基聚硅烷　(PhSiMe　) n为原料 ,在无水AlCl3 存在下 ,通过与酰氯、酸酐及酯的取代反应合成了氯代聚硅烷及一系列共聚物 .在乙酰氯的作用下 ,　(PhSiMe　) n上的苯基能够被近乎完全的取代而生成氯代聚硅烷 .一元酸酐 (乙酸酐和丙酸酐 )在用酰氧基部分取代聚硅烷上苯基的同时 ,进行得更多的还是Cl取代 .而顺丁烯二酸酐、邻苯二甲酸酐和乙酸乙酯则只进行不完全的Cl取代 ,根据分子活性的不同得到取代比率各不相同的共聚物 .初步分析了各反应的过程 ,讨论了影响反应的因素 ,同时对于各产物的荧光和紫外特性也进行了分析和讨论     

The thermal degradation of polysiloxanes—Part 4: Poly(dimethyl/diphenyl siloxane)

Poly(dimethyl/diphenyl siloxanes) have been prepared with a range of phenyl group contents both from mixtures of dimethyl and diphenyl cyclic siloxanes and from cyclic siloxanes in which both dimethyl and diphenyl structures are present. Attempts to prepare poly(diphenyl siloxane) with a reasonably high molecular weight were unsuccessful.The products of degradation of the poly(dimethyl/diphenyl siloxanes) are benzene and complex mixtures of cyclic oligomers which have been separated, identified and analysed. The characteristics of the formation of these products are discussed in relation to the degradation reactions which occur in poly(dimethyl siloxane), poly(methyphenyl siloxane) and poly(dimethyl/methylphenyl siloxane) and which have been described previously.     

Dynamics of positive charge carriers on Si chains of polysilanes

The transient absorption of radical cations of a variety of substituted polysilanes is discussed quantitatively in terms of the molar extinction coefficient and oscillator strength by nanosecond pulse radiolysis. Oxygen-saturated polysilane solutions in benzene exhibit a strong transient absorption band ascribed to the polysilane radical cation. The transient species react with N,N,N',N'-tetramethyl-p-phenylene-diamine (TMPD) to produce TMPD radical cations. On the basis of the molar extinction coefficient of the TMPD radical cation, the molar extinction coefficients for the radical cations of polysilanes are found to increase in the range 3.3 x 10(4) to 2.0 x 10(5) M(-)(1) cm(-)(1) with increasing polymer segment length. The stepwise increase in the total oscillator strength with an increase in the number of phenyl rings directly bonded to the Si skeleton suggests the delocalization of the positive polaron state and/or the SOMO state over the phenyl rings, indicating the importance of phenyl rings in intermolecular hole transfer processes.     

Photoconductive Polysilanes Bearing Charge-photogenerating Groups Based on Carbazole. 2 Synthesis via the Chemical Modification of Poly(alkylphenylsilane)s

The chemical modification of poly(alkylphenylsilane)s via the partial dearylation by reaction with triflic acid followed by the nucleophilic substitution of triflate groups by carbazolyllithium and 4-(9-carbazolyl)phenyllithium was applied to poly(methylphenylsilane)s and poly(ethylphenylsilane)s prepared under various experimental conditions in order to obtain polysilanes exhibiting photoconductive properties combining the high charge-photogenerating quantum yield of poly(vinylcarbazole) and the high charge-carrier mobility of polysilanes. Polymers containing 7–20% of the desired unit bearing the potential charge photogenerating site were synthesized by this way. The strong degradation of the Si chain induced by triflic acid limits the molecular weight and, in some cases, the amount of isolated derivatized polysilanes. When the charge-photogenerating sites are conjugated with the Si chain, the corresponding polysilanes doped with 2,4,7-trinitro-9-fluorenone (TNF) may exhibit improved photoconductive properties compared with those observed for the poly(vinylcarbazole)/TNF system. © 1997 John Wiley & Sons, Ltd.     

Visible absorption of iodine-doped polysilane with p-N,N-dialkylaminophenyl substituents

The doping effects on optical and electrical properties of polysilanes were investigated by in-situ measurement. When polysilanes bearing a p-N,N-dialkylaminophenyl substituent were doped with iodine vapor, drastic spectral changes were observed. The evolved visible absorption up to 700 nm was found to be strong and stable compared to that of iodine-doped polysilanes such as poly(methylphenylsilane). On the basis of the studies concerning iodine doping of the related p-N,N-dimethylaminophenyl-substituted silane and disilane, and also theoretical calculations, this new absorption can be best interpreted by the result of charge transfer consisting of the strong interaction between iodine and dialkylamino substituents in the polysilanes. © 1996 John Wiley & Sons, Inc.     

Anionic synthesis of binary random in-chain multi-functionalized poly(styrene/butadiene/isoprene and dimethyl [4-phenylvinyl)-phenyl]silane)(PS-DPESiH,PB-DPESiH,PI-DPESiH) copolymers

The binary random in-chain silyl-hydride multi-functionalized poly(styrene/butadiene/isoprene and dimethyl[4-(1-phenylvinyl) phenyl]silane)(PS-DPESiH,PB-DPESiH,PI-DPESiH) copolymers were successfully synthesized.These functionalized copolymers were prepared in hexane with n-BuLi as the initiator at 50℃for 4 h.The silyl-hydride groups were introduced into polymer backbones quantitatively by living anionic polymerization.The copolymers were determined through ’H NMR,size exclusion chromatography(SEC) and differential scanning calorimetry(DSC) techniques,while the number of silyl-hydride groups was calculated and discussed.     

顺式和反式-2-氨基-3-氰基-4-苯基-1-(4'-甲基苯基)-2-环戊烯-1-醇的合成和晶体结构

用低价钛试剂(TiCl4-Zn)与4, 4-二氰基-3-苯基-1-(4'-甲基苯基)-1-丁酮反应合成了顺式和反式-2-氨基-3-氰基-4-苯基-1-(4'-甲基苯基)-2-环戊烯-1-醇, 并用X射线衍射分析确定了这两个异构体的构型。     

Determination of stability and degradation in polysilanes by an electronic mechanism

Polysilanes are potential candidates for active materials in light emitting diodes because of possible emission in the near-ultraviolet to blue region. Unfortunately, they degrade rapidly upon exposure to light because of scission of sigma bonds. Relative stability of four polysilanes, for example, poly(di-n-butylsilane) (PDBS), poly(di-n-hexylsilane) (PDHS), poly(methylphenylsilane) (PMPS), and poly[bis(p-butylphenyl)silane] (PBPS), which have been reported as active materials in light emitting diodes, have been investigated theoretically through semiempirical (AM1) and ab initio (HF/6-31g) methods and density functional theory using B3LYP parametrization. The AM1 level of calculation predicts the absorption maxima reasonably, but it fails to explain the relative stabilities of the four polysilanes in the excited state. However, calculations based on configuration interaction with single excitation and time-dependent density functional theory suggest additional stabilization in the excited states through intersystem crossing to triplets for PMPS and PBPS, consistent with the experimental observation. In contrast, no such stabilization is predicted for PDBS and PDHS. Furthermore, the existence of a stable triplet state in PMPS may also explain the visible emission observed experimentally in PMPS.     

SYNTHESIS AND OPTICAL-ELECTRONIC PROPERTIES OF POLY [METHYLTETRAPHENYLPHENYLSILYLENE-CO- BIS（METHYLPHENYLSILYL）ACETYLENE]

Poly(methyltetraphenylphenylsilylene-co-bis(methylphenylsilyl)acetylene) (PSA) was synthesized by the cocondensation reaction of methyltetraphenylphenyldichlorosilane and bis(chloromethylphenylsilyl)acetylene with sodium in toluene. The PSA thus obtained was soluble in most organic solvents, and its molecular weight was smaller than that of poly[(disilanylene)acetylenes] with alkyl- or aryl-substitution because of the great steric congestion of tetraphenylphenyl groups. The optical and electronic properties of the polymer were investigated. The results show that PSA has strong UV absorption and fluorescence emission, the maximum UV absorption wavelength of PSA is 330 nm, which shows a considerable red-shift in comparison with that of poly(methylphenylsilylene-co-methylphenylsilylacetylene) (PSI) and alkylsubstituted poly[(disilanylene)acetylenes]. A strong photoluminescence band at 470 nm in THF and 432 nm in benzene can be observed in the visible region, respectively. Treatment of the films of PSA with I2 vapor afforded conducting films. The conductivity of PSA thin film doped with I2 was measured to be 0.35 Scm-1 in the air which is lower than that of poly(methyltetraphenylphenylsilylene-co-bis(methylphenylsilyl)phenylene), but higher than that of σ-π polymers without tetraphenylphenyl groups. As an explanation, the tetraphenylphenyl group is a large π-electron-conjugated group; after being introduced to the Si atoms of the polysilanes, the interaction between π-electrons of the tetraphenylphenyl groups and the σ-electrons conjugated along the Si-Si bonds is increased strongly, and the σ-electrons can be conjugated more extensively along the main chain of the polysilanes.     

Functionalized poly(methylphenyl)silane: End group reactivity

A Cl ended poly(methylphenyl) silane is synthesized and analyzed by ²⁹Si-NMR spectroscopy. The end groups are extremely reactive with small compounds as alcohols and amines. By this way, copolysilanes containing some nitrogen atoms can be synthesized. © 1996 John Wiley & Sons, Inc.