具有聚集诱导发光特性含萘单元共轭聚合物的合成

Synthesis of Conjugated Polymers Containing Naphthalene Units with Aggregation Induced Emission Characteristics

首先氯化亚砜和2,6-萘二甲酸酰氯化反应合成2,6-萘二甲酰氯(M1),然后M1和叔丁基苯傅-克酰基化反应合成2,6-二(4-叔丁基苯甲酰基)萘(M2),进而与1,2-乙二硫醇合成2,6-双(2-(4-(叔丁基)苯基)-1,3-二巯基-2-基)萘(M3),最后以六羰基钨为催化剂,分子间脱硫反应制备含萘单元共轭聚合物PNTB。利用傅里叶变换红外光谱仪、核磁共振波谱仪、凝胶渗透色谱仪、紫外-可见分光光度计和荧光分光光度计对M2、M3和PNTB的化学结构、相对分子质量和光学性质进行测试与表征。结果表明,随四氢呋喃/水(THF/H2O)混合溶剂中水分数不断增加,PNTB的荧光强度呈递增的趋势,表明PNTB具有聚集诱导发光特性。PNTB在溶液状态(THF为溶剂)和聚集状态(THF/H2O,体积比10/90)的荧光量子产率分别为1.83%和12.74%,说明PNTB容易发生聚集,聚集诱导发光效果良好。

Firstly,2,6-naphthalenedicarbonyl dichloride(M1)was prepared by acylation reaction using thionyl chloride and 2,6-naphthalenedicarboxylic acid as starting material,then compound 2,6-bis-(4-tertbutylbenzoyl)naphthalene(M2)was synthesized using Ml and tert-butylbenzene by Friedel-Crafts reaction,and compound 2,6-bis(2-(4-(tert-butyl)phenyl)-1,3-dithiolan-2-yl)naphthalene(M3)was synthesized with M2 and 1,2-ethanedithiol.Finally,conjugated polymer PNTB containing naphthalene units was prepared by intermolecular desulphurization.The chemical structure,molecular weight and optical properties of M2,M3 and PNTB were tested and characterized through Fourier transform infrared spectrometer,nuclear magnetic resonance spectrometer,gel permeation chromatograph,ultraviolet visible spectrophotometer and fluorescence spectrophotometer,respectively.The results show the fluorescence intensity of PNTB is increased with the water fraction increasing from 0%to 90%in the THF/H2O mixed solvent.The fluorescence quantum yields of PNTB,in solution state(THF as solvent)and aggregation state(THF/H2O,volume ratio of 10/90)are 1.83%and 12.74%,respectively,indicating that PNTB is more likely to aggregate and the aggregation-induced emission effect is good.