摘要
以1,5-二羟基蒽醌、4-硝基邻苯二甲腈、3,5-二甲基苯酚、β-萘酚为主要原料,合成了3种不同的邻苯二甲腈衍生物前驱体,再经1,8-二氮杂双环[5.4.0]十一碳-7-烯催化聚合成9(10),16(17),23(24)-三[3,5-二甲基苯氧基]-2(3)-(1,5-二氧基蒽醌)双核锌酞菁(D-CPc)和9(10),16(17),23(24)-三[β-萘氧基]-2(3)-(1,5-二氧基蒽醌)双核锌酞菁(β-CPc)。利用FT-IR、UV-Vis、1H-NMR、元素分析、循环伏安法对2种化合物的特性进行了表征。结果表明,D-CPc和β-CPc的Q带分别发生11、10 nm的红移,在400~600 nm范围内表现出明显的紫外光谱吸收,弥补了无取代酞菁在400~600 nm范围内无吸收的缺陷,并且在0.1×10^-5~1.0×10^-5mol/L的DMF溶液中表现出良好溶解性。循环伏安法研究表明,D-CPc和β-CPc的ELUMO值分别为-3.17、-3.26 eV,EHOMO值分别为-5.16、-5.10 eV,与TiO2能级和氧化还原电对能级相匹配,满足能带间隙规则,能够实现染料的氧化还原。
Three kinds of phthalonitrile derivatives precursors are synthesized with 1,5-dihydroxyanthraquinone,4-nitrophthalonitrile,3,5-dimethylphenol andβ-naphthol as main raw materials.The precursors are then catalyzed by DBU to form 9(10),16(17),23(24)-tris[3,5-dimethylphenoxy]-2(3)-(1,5-dioxyanthraquinone)binuclear zinc phthalocyanine(D-CPc)and 9(10),16(17),23(24)-tris[β-naphthoxy]-2(3)-(1,5-dioxyanthraquinone)binuclear zinc phthalocyanine(β-CPc).Two compounds prepared are fully characterized by FT-IR,UV-Vis,1 HNMR,elemental analysis,and cyclic voltammetry.It is shown that Q bands of both D-CPc andβ-CPc undergo 11 nm and 10 nm of red shift,respectively.Both compounds exhibit obvious absorption in the range of 400-600 nm,while non-substituted phthalocyanine shows no-absorption in the range of 400-600 nm.They also show an excellent solubility in 0.1×10^-5-1.0×10^-5 mol·L-1 DMF solution.Cyclic voltammetry studies show that ELUMOvalues of D-CPc andβ-CPc are-3.17 and-3.26 eV,respectively,and their EHOMOvalues are-5.16 and-5.10 eV,respectively.They can match with TiO2 energy level and redox electric pair energy level,meet band gap rules,and realize redox of dyes.
作者
徐康
周雪飞
王秀秀
张学俊
XU Kang;ZHOU Xue-fei;WANG Xiu-xiu;ZHANG Xue-jun(School of Science,North University of China,Taiyuan 030051,China)
出处
《现代化工》
CAS
CSCD
北大核心
2020年第5期117-121,127,共6页
Modern Chemical Industry
基金
山西省回国留学人员科研资助项目(2015-078)
山西省自然科学基金资助项目(2015011011)。
关键词
双核酞菁
蒽醌
紫外光谱
能带间隙
binuclear phthalocyanine
anthraquinone
UV spectrum
band gap
