主链含2,3-二(4'-辛氧基苯基)喹喔啉单元窄带隙共聚物的合成及性能

Synthesis and Properties of Narrow Bandgap Copolymers Containing 2,3-Bis(4-octyloxyphenyl) quinoxaline Unit in Main Chain

以二(三苯基膦)二氯化钯[Pd(PPh3)2Cl2]或醋酸钯[Pd(OAc)2]与三环己基膦作为催化剂,通过Sonagashira或Suzuki碳-碳偶联反应制备了3种含2,3-二(4'-辛氧基苯基)-5,8-二硒吩基喹喔啉单元的聚苯撑乙炔类(P1)、聚芴类(P2)和聚咔唑类(P3)π-共轭交替共聚物。经傅里叶变换红外光谱、氢核磁共振谱、紫外-可见光谱、荧光光谱、循环伏安、X射线粉末衍射、热重和凝胶渗透色谱等测试手段对其进行了表征并研究共聚物在CHCl3-CF3COOH混合溶液中的酸致变色行为。结果表明,得到的共聚物在甲苯、氯仿、四氢呋喃等有机溶剂里具有很好的溶解性,3种共聚物在CHCl3和薄膜状态下长波长处的紫外-可见最大吸收波长分别在546 nm、542 nm、538 nm和586 nm、552 nm、558 nm处出现。共聚物的光学能隙分别为1.80 e V、1.86 e V和1.84 e V。与P1和P2相比,P3显示较好的酸致变色行为并且三氟乙酸浓度在1.346×10-3~13.46×10-3mol/L范围之间其表现出酸浓度与吸光度之间的线性关系。通过循环伏安测试,共聚物均具有一定的p掺杂和空穴传输行为。

π-Conjugated alternating copolymers containing 2,3-bis（4-octyloxyphenyl）-5,8-bis（seleno-phen-2-yl）quinoxaline as poly（phenylene ethynylene） s（P1）,polyfluorenes（P2） and polycarbazoles（P3） were prepared by Sonogashira or Suziki C-C coupling reactions using Pd（PPh3）2 Cl2 or Pd（OAc）2 and tricyclohexylphosphine as catalyst,respectively. The structures of copolymers were performed by FT-IR,1 H-NMR,ultraviolet and visible spectrophotometry（UV-vis）,fluorescence spectroscopy（PL）,gel permeation chromatography（GPC）,cyclic voltammogram（CV） and XRD,and acidichromic properties of all copolymers were studied in CHCl3-CF3 COOH mixtures. The results show that all copolymers are soluble in common organic solvents such as toluene,CHCl3 and tetrahydrofuran（THF）,and the maximum absorption at long wavelength appears at 546 nm,542 nm and 538 nm in CHCl3 solution,and 586 nm,552 nm,558 nm in film state. The optical band gap energy of copolymers is 1.80 e V,186 e V and 1.84 e V,respectively. Comparing with P1 and P2,copolymer P3 displays better acidochromic sensitivity and linear relationship between absorbance and concentration with the concentration of CF3 COOH from 1.346× 10-3 mol/L to 13.46× 10-3 mol/L. Electrochemical behaviors of polymers depict p-doping and some hole-transporting properties.