聚芳撑乙炔微孔骨架材料的合成及其气体吸附

有机微孔聚合物（MOPs）在气体存储、吸附分离和非均相催化等领域具有优良性质而广受关注.近年来,聚芳撑乙炔微孔骨架材料的研究成为MOPs领域中的热点.分别以三（4-乙炔基）苯胺、甲基三（4-乙炔基苯基）硅烷、苯基三（4-乙炔基苯基）硅烷为基本构筑单元,通过端炔基氧化均聚的方法,制备了三种聚芳撑乙炔微孔骨架材料,研究了结构组成对制备聚合物孔道性能和气体吸附性能的影响.氮气吸附测试结果表明,聚合物的Brunauer-Emmett-Teller （BET）比表面积的范围在602~715 m²·g^-1.由于骨架中含有富氮基团（三苯胺）以及具有较大的比表面积,在1.13 bar/273 K条件下,聚三（4-乙炔基）苯胺（TEPA-MOP）的CO₂吸附能力为1.59 mmol·g^-1.此外,TEPA-MOP和聚苯基三（4-乙炔基苯基）硅烷（TEPP-MOP）具有优良的选择性吸附性能,对CO₂/N₂的选择性吸附分别是69.9和73.2.聚合物TEPA-MOP具有优异的CO₂/N₂的选择吸附性和适中的CO₂吸附能力,因此将在气体吸附与分离方面具有潜在的应用前景.     

Self-assembled structures with liquid-crystalline order in aqueous solution by patterning poly(phenylene ethynylene)s

Facially amphiphilic (FA) phenylene ethynylene (PE) polymers that self-assemble in aqueous solution were studied by small-angle X-ray diffraction (SAXD) and found to self-assemble into bilayers with a fully extended backbone. The resulting bilayers have long-range liquid-crystalline order. This self-assembly is programmed into the molecule by placing polar and nonpolar groups at precise locations so that they segregate onto opposite sides of the molecular structure. The absence of FA patterning generated an amorphous sample confirming the importance of this programmed amphiphilicity in the self-assembly process. Facially amphiphilic patterning represents a new design criterion for supramolecular chemistry, illustrated here in the observation of molecular ordering into bilayers reminiscent of self-assembled structures commonly found in biology, including amphiphilic beta-sheet polypeptides and phospholipid bilayers.     

Poly(p‐phenylene ethynylene) Incorporating Sterically Enshrouding m‐Terphenyl Oxacyclophane Canopies

A sterically encumbered m‐terphenyl oxacyclophane substituted with two aryl iodide substituents has been prepared as a versatile monomer for the preparation of π‐conjugated polymers. The monomer has been used to prepare a poly(p‐phenylene ethynylene) derivative (P1) incorporating oxacyclophane units as canopies that shield one side of the π‐system from inter‐chain interactions. The photophysical properties of P1 in dilute solution compare well to those of a poly(p‐phenylene ethynylene) derivative (P2) that lacks the canopy. The presence of the steric canopy leads to a diminished inter‐chain interaction in the solid state and enhances the kinetic response of P1 to vapors of nitro‐organics such as TNT, presumably by increasing the permeability of P1 to these analytes over that of P2.

     

Preparation and properties of poly(dimethysilyleneethynylenephenylene‐ethynylene)/graphene Composites

Polymer composites with carbon‐based nano‐fillers have generated significant interest in industry and science because of their multifunctional and valuable properties. An APA‐functionalized GO nanofiller (GO–APA) was prepared through the reaction between graphene oxide (GO) and 3‐aminophenyl acetylene (APA) in dimethylformide (DMF) with ammonia hydroxide. Furthermore the PDSEPE/GO–APA composites were made from Poly(dimethysilyleneethynylenephenylene ethynylene) (PDSEPE) and GO–APA. FT‐IR, XRD, XPS, SEM, DSC and TGA techniques were used to characterize the chemical compositions and physical and chemical properties of GO–APA and PDSEPE/GO–APA composites. As a result, the prepared PDSEPE/GO–APA composites show high thermal stabilities, excellent electrical conductivity and good flexural strength. When the weight percentage of GO–APA reaches 0.5%, the PDSEPE/GO–APA composite electrical conductivity increases by 6 orders of magnitude and the flexural strength improves by nearly 33% compared with that of cured PDSEPE resin. Copyright © 2015 John Wiley & Sons, Ltd.     

聚对苯撑乙炔咔唑薄膜对TNT挥发物的检测

以3, 6-二溴-9-辛基咔唑和2, 5-二戊烷氧基-1, 4-二乙炔基苯为单体,通过Pd催化的Sonogashira偶联反应合成了聚对苯撑乙炔咔唑衍生物PPECz。PPECz的溶液和固体薄膜都具有较好的发光性能,并且均对2, 4, 6-三硝基甲苯(TNT)有明显的响应。在常温常压条件下,微量(40 μg)的TNT挥发物在60 s内就能使聚合物PPECz薄膜的荧光强度被猝灭56%,可作为一种潜在的硝基苯类爆炸物的荧光检测材料。     

Absorption and emission properties of phenylene ethynylene oligomers: effect of substitution and π-conjugation length

The optical properties of a series of π-conjugated phenylene-ethynylene oligomers (OPEs) have been studied by advanced quantum chemical methods. The ground state and lowest singlet excited state geometries of unsubstituted and different electron donor and acceptor groups substituted OPEs are optimized by density functional theory and configuration interaction singles methods. The absorption and emission spectra of unsubstituted and substituted OPEs have been calculated using the time-dependent density functional theory (TDDFT) method. The results of theoretical calculations are in good agreement with the available experimental results. It has been found that the substitution of electron donating and withdrawing groups in the phenyl ring and conjugation length of the OPEs has significantly affect both the absorption and emission spectra     

一种侧基横挂偶极单元的聚苯撑乙炔的光学性质

以对苯二乙炔和2,5-二溴苯衍生物为单体,无水N,N-二甲基甲酰胺（DMF）为溶剂,通过Sonogashira偶联反应,采用2种Pd催化剂（Pd(PPh₃)₄和PdCl₂(PPh₃)₂）合成了一种侧基带有偶极基团的聚苯撑乙炔。 单体的化学结构通过IR、NMR和元素分析等测试技术得到确证。 聚合物外观为黄色粉状固体,室温下溶于CHCl₃和THF等有机溶剂。 2种Pd催化剂对合成聚合物的分子量以及光学性质影响不大,但对聚合物的发光效率影响较大,由Pd(PPh₃)₄催化得到的聚合物分子链具有较高的立构规整性,因此,具有较高的发光效率。 不同溶剂环境以及聚合物固体膜的紫外以及荧光光谱研究结果表明,侧基偶极基团的相互静电排斥力,可以有效阻止大分子链之间的聚集,从而有效地抑制了聚苯撑乙炔聚集体的形成。     

Meta‐linked and para‐linked water‐soluble poly(arylene ethynylene)s with amino acid side chains: Effects of different linkage on Hg2+ ion sensing properties in aqueous media

Water‐soluble, meta‐ and para‐linked poly(arylene ethynylene)s containing L ‐aspartic acid‐functionalized fluorene units (P1 and P2) and their model compounds (M1 and M2) have been synthesized, and their photophysical properties and fluorescent sensing properties were investigated in aqueous solution. P1 and M1 with the meta‐linkage show blue‐shifted absorption and emission spectra, and decreased photoluminescence quantum yields compared with those of P2 and M2 with para‐linkage. Their absorption and fluorescence spectra are pH dependent perhaps due to the aggregation of the polymer chains at low pH values. In buffer solutions, both polymers and their model compounds exhibit the excellent selectivity and sensitivity to Hg²⁺ over other common metal ions. Furthermore, the quenching constant and detection limit of P1 are determined to be 1.04 × 10⁷ M^?1 and 10 nM, and show the higher sensitivity compared to P2. Further comparison of their model compounds reveal that the sensitivity and quenching efficiency of M1 is also higher than that of M2, indicating that the meta‐linkage pattern plays a key role in improving their Hg²⁺ ion sensing properties. In addition, both meta‐ and para‐linked polymers exhibit the higher quenching efficiency than their model compounds due to the amplified fluorescence response of conjugated polymer. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Hyperbranched poly(arylene ethynylene)s with triphenylamine core for polymer light‐emitting diodes

A series of light‐emitting hyperbranched poly(arylene ethynylene)s (HB‐PAEs) were prepared by the Sonogashira coupling from bisethynyl of carbazole, fluorene, or dialkoxybenzenes (A₂ type) and tris(4‐iodophenyl)amine (B₃ type). For comparison, two linear polymers (L‐PAEs) of the HB analogs were also synthesized. The polymers were characterized by Fourier transform infrared, NMR, and GPC. The HB polymers showed excellent solubility in chloroform, THF, and chlorobenzene when compared with their linear analogs. The number‐average molecular weight (M_n) of the polymers determined from GPC was found to be in the range of 18,600–34,200. The polymers were thermally stable up to 298–330 °C with only 5% weight loss. The absorption maxima of the polymers were between 354 and 411 nm with optical band gap in the range of 2.5–2.9 eV. The HB polymers were found to be highly fluorescent with photoluminescence quantum yields around 33–42%. The highest occupied molecular orbital energy levels of the polymers calculated from onset oxidation potentials were found to be in the range from ?5.83 to ?6.20 eV. Electroluminescence (EL) properties of three HB‐PAEs and one L‐PAE were investigated with device configuration ITO/PEDOT:PSS/Polymer/LiF/Al. The EL maxima of HB‐PAEs were found to be in the range of 507–558 nm with turn‐on voltages around 7.5–10 V and maximum brightness values of 316–490 cd/m². At the same time, linear analog of one HB‐PAE was found to show a maximum brightness of 300 cd/m² at a turn‐on voltage of 8.2 V. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011