脱氢枞酸三芳胺基丙烯腈化合物的合成及其光物理性能研究  

Dehydroabietic Acid Triarylamine-based Acrylonitrile Compounds:Synthesis and Photophysical Properties

作　　者：高亚楠 窦立薇 宋杰[4] 高宏[1,3] 商士斌[1,3] 宋湛谦 GAO Yanan;DOU Liwei;SONG Jie;GAO Hong;SHANG Shibin;SONG Zhanqian(Institute of Chemical Industry of Forest Products,CAF,National Engineering Lab.for Biomass Chemical Utilization,Key Lab.of Chemical Engineering of Forest Products,National Forestry and Grassland Administration,Key Lab.of Biomass Energy and Material,Jiangsu Province,Nanjing 210042,China;Jiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources,Nanjing Forestry University,Nanjing 210037,China;Research Institute of Forestry New Technology,CAF,Beijing 100091,China;Department of Chemistry and Biochemistry,University of Michigan-Flint,Flint 48502,USA)

机构地区：[1]中国林业科学研究院林产化学工业研究所,生物质化学利用国家工程实验室,国家林业和草原局林产化学工程重点实验室,江苏省生物质能源与材料重点实验室,江苏南京210042 [2]南京林业大学江苏省林业资源高效加工利用协同创新中心,江苏南京210037 [3]中国林业科学研究院林业新技术研究所,北京100091 [4]密歇根大学弗林特分校化学与生物化学系,美国弗林特48502

出　　处：《林产化学与工业》2022年第3期10-18,共9页Chemistry and Industry of Forest Products

基　　金：国家自然科学基金资助项目(31670576)。

摘　　要：以5-脱氢枞酸三苯胺-噻吩-2-甲醛与3,5-双(三氟甲基)苯乙腈为原料,分别在常温和加热回流的条件下反应,得到2个脱氢枞酸三芳胺基丙烯腈化合物:甲基(Z)-6-((4-(5-(2-(3,5-双(三氟甲基)苯基)-2-氰基乙烯基)噻吩-2-基)苯基)(4-甲氧基苯基)氨基)-7-异丙基-1,4a-二甲基-1,2,3,4,4a,9,10,10a-八氢菲-1-羧酸盐(2)和二甲基6,6'-(((1-氰基乙烯-1,2-二基)双(噻吩-5,2-二基))双(4,1-苯撑)双(4-甲氧基苯基)氮杂二烯基)(E)-双(7-异丙基-1,4a-二甲基-1,2,3,4,4a,9,10,10a-八氢菲-1-羧酸盐)(3)。探讨了化合物2和3的紫外吸收光谱、荧光发射光谱、溶致变色效应、聚集诱导发光(AIE)特性、热稳定性及电化学性能,并通过理论计算对其结构与性能的关系进行了进一步分析。研究结果表明:与三芳胺基丙烯腈化合物相比,引入脱氢枞酸骨架后,化合物表现出更大的斯托克斯位移、固体状态下更长的红光发射;化合物2表现出AIE特性,而化合物3不具有AIE特性;这两个化合物均具有较好的热稳定性和形态稳定性。脱氢枞酸骨架的引入使得2和3获得了更高的HOMO、LUMO能级,以及窄的带隙值。Compounds methyl(Z)-6-((4-(5-(2-(3,5-bis(trifluoromethyl)phenyl)-2-cyanovinyl)thiophen-2-yl)phen-yl)(4-methoxyphenyl)amino)-7-isopropyl-1,4a-dimethyl-1,2,3,4,4a,9,10,10a-octahydrophenanthrene-1-carboxylate(2)and dimethyl 6,6'-(((1-cyanoethene-1,2-diyl)bis(thiophene-5,2-diyl))bis(4,1-phenylene))bis((4-methoxyphen-yl)azanediyl))(E)-bis(7-isopropyl-1,4a-dimethyl-1,2,3,4,4a,9,10,10a-octahydrophenanthrene-1-carboxylate)(3)were obtained simply by mixing 5-(dehydroabietic acid triarylamine)-thiophene-2-carbaldehyde and 3,5-bis(trifluoromethyl)phenylacetonitrile at room temperature and 100℃,respectively.The UV-Vis absorption spectra,fluorescence emission spectra,solvatochromism effect,aggregation-induced emission(AIE)characteristics,thermal stability and electrochemical performance of compounds are studied,and the relationship between their structure and performance is further studied through theoretical calculations.Compared with triarylamine-based acrylonitrile compounds,after introducing the dehydroabietic acid skeleton,the compounds show a larger stokes shift and longer red light emission in the solid state.2 exhibits AIE characteristics,while 3 does not have AIE characteristics.Both of the two compounds have good thermal stability and morphological stability.2 and 3 have higher highest occupied molecular orbital(HOMO),lowest unoccupied molecular orbital(LUMO)energy levels and narrow band gap,due to the introduction of dehydroabietic acid skeleton.

关 键 词：脱氢枞酸三芳胺 丙烯腈 光物理性能 聚集诱导发光 

分 类 号：TQ35[化学工程] O657[理学—分析化学]