单分散的还原态和中间氧化态聚苯胺齐聚物的合成与紫外光谱研究

Synthesis of Monodisperse Pheyl-capped Oligoaniline Pentamer and Hexamer in the Leucoemeraldine Oxidation State and EB State and Its UV Studies

提出了一条合成苯胺齐聚物的新路线 :由高氧化态的苯胺四聚体与二苯胺或 N-苯基 - 1,4 -对苯二胺反应合成苯基封端的苯胺五聚体和六聚体 ,用红外、质谱、核磁共振、基底辅助激光解吸质谱 (MAL DI- MS)进行了表征 .提出一条可能的机理 ,即高氧化态的苯胺四聚体与二苯胺或N -苯基 - 1,4 -对苯二胺在酸性溶液中混合时 ,四聚体、二苯胺和 N -苯基 - 1,4 -对苯二胺的分子中均形成阳离子自由基 ,四聚体的阳离子自由基与后二者的阳离子自由基耦合形成苯胺五聚体和六聚体 .还原态的苯胺齐聚物氧化成中间氧化态的苯胺齐聚物 ,使用硫酸铵和六水和三氯化铁等氧化剂能打断苯胺五聚体和六聚体的分子链 .实验发现 ,氧化银是将还原态苯胺齐聚物氧化成中间氧化态的齐聚物的最好的氧化剂 .用紫外可见光谱对中间氧化态的五聚体和六聚体进行了研究 。

Aniline pentamer and hexamer in the leucoemeraldine oxidation state were synthesized through a novel method. The method was accomplished by the reaction of parent aniline tetramer in the pernigraniline oxidation state with diphenylamine and N phenyl 1,4 phenylenediamine in the leucoemeraldine oxidation state respectively. The oligomers in the leucoemeraldine oxidation state were characterized by IR, NMR, elemental analysis and MALDI MS. Aniline pentamer and hexamer in the emeraldine oxidation state were synthesized by the oxidation of Ag 2O in DMF. It was found that some fragmentation occurred when the pentamer and hexamer were oxidized by (NH 4) 2S 2O 8 and FeCl 3·6H 2O. The pentamer and hexamer in the emeraldine oxidation state was studied by UV/Vis spectra. The relative intensity of exciton peak for pentaaniline showed a little increase compared with that of hexaaniline.