小分子脂肪酮亚胺的光致发光行为  

Photoluminescence behaviors of small aliphatic ketimines

作　　者：张亲 白云浩 庄佩凤 赵雅馨 汪辉亮 Qin Zhang;Yunhao Bai;Peifeng Zhuang;Yaoxin Zhao;Huiliang Wang(Beijing Key Laboratory of Energy Conversion and Storage Materials,College of Chemistry,Beijing Normal University,Beijing 100875,China;Institute of Coal Chemistry,Chinese Academy of Sciences,Taiyuan 030001,China)

机构地区：[1]北京师范大学化学学院能量转换与存储材料北京市重点实验室,北京100875 [2]中国科学院山西煤炭化学研究所,太原030001

出　　处：《中国科学：化学》2022年第6期980-988,共9页SCIENTIA SINICA Chimica

基　　金：国家自然科学基金(编号:21574015)资助项目。

摘　　要：非传统有机发光材料因其独特的发光行为和发光机理近年来受到越来越多的关注.一些芳香族亚胺类化合物(席夫碱)已被发现具有聚集诱导发光的行为,但还没有关于小分子脂肪酮亚胺发光行为的报道.本工作发现多种小分子脂肪伯胺与丙酮在室温下反应就可以得到具有强荧光发射的产物,其荧光发射随反应时间增加而增强,且其最大激发波长和发射波长均发生显著的红移,最大发射波长超过600 nm.对各种伯胺和丙酮反应产物的结构表征证实均生成了脂肪酮亚胺化合物.脂肪酮亚胺化合物表现出浓度增强荧光发射行为,随浓度的增大,荧光强度增大且荧光发射红移.酮亚胺的荧光发射具有聚集增强特性,其聚集体尺寸随浓度增大而增大.酮亚胺的荧光发射还对溶剂等刺激有响应.理论计算结果显示,随聚集分子数增加,聚集体的HOMO–LUMO能级差逐渐减小.该研究拓展了非典型发光物质的范围,具有潜在的应用价值.Non-traditional organic luminescent materials have attracted more and more attention in recent years because of their unique luminescent behaviors and mechanisms. Some aromatic imines(Schiff bases) have been found to exhibit aggregation-induced emission behaviors, but there is no report on the luminescence behavior of small aliphatic ketimines yet. This work reports that aliphatic primary amines easily react with acetone at room temperature, producing products with very strong fluorescence emissions. The fluorescence intensity increases with the increasing reaction time,and the maximum excitation and emission wavelengths red-shift significantly, with the maximum emission wavelengths more than 600 nm. Structural characterizations prove that the fluorescent products are aliphatic ketimines. These compounds exhibit concentration-enhanced emission behaviors. Their fluorescence intensity increases and the emission red-shifts with the increasing concentration. The aliphatic ketimines show aggregation-enhanced emissions, and the aggregate particle size increases with the increase of concentration. The fluorescence emission of the ketimines is also sensitive to solvents. Theoretical calculation results show that the HOMO–LUMO energy gap of ketimine aggregates decreases with the increase of the number of the aggregated molecules. This study expands the scope of non-traditional luminescent materials and may have potential practical applications.

关 键 词：非传统发光化合物 脂肪酮亚胺 聚集增强发光 荧光 

分 类 号：O622.6[理学—有机化学]