Synthesis of Fluorene-Bridged Arylene Vinylene Fluorophores： Effects of End-Capping Groups on the Optical Properties, Aggregation Induced Emission  

作　　者：Guo-Feng Zhang Tao Chen Ze-Qiang Chen Matthew P. Aldred Xianggao Meng Ming-Qiang Zhu 

机构地区：[1]Wuhan National Laboratory for Optoelectronics, School of Optical and Electronic Information, Huazhong University of Science and Technology, Wuhan, Hubei 430074, China [2]Department of Chemistry, Durham University, South Road, Durham DH1 3LE, UK [3]Key Laboratory of Pesticide and Chemical Biology of Ministry of Education, College of Chemistry, Central China Normal University, Wuhan, Hubei 430079, China

出　　处：《Chinese Journal of Chemistry》2015年第8期939-947,共9页中国化学（英文版）

摘　　要：We have synthesized a series of fluorene-based fluorophores, in which a central fluorene core has been modified with different peripheral arylene vinylene substituents that are able to activate aggregation-induced emission （AIE） characteristics. 9,9-Dioctylfluorene doubly end-capped at the 2,7-positions with triphenylethene groups, such as 4-（2,2-diphenylvinyl）phenyl （F1-（2,2）-HTPE） and 4-（1,2-dipbenylvinyl）phenyl （F1-（1,2）-HTPE） were synthesized and compared to the tetraphenylethene analogue （F1-TPE）. Both FI-（2,2）-HTPE and F1-（1,2）-HTPE glow with a deep blue fluorescence in THF solution with emission maxima （λem） of 426 and 403 nm, respectively. The λem slightly red-shifts in the solid-state to 458 nm for F 1-（2,2）-HTPE and 437 nm for F 1-（1,2）-HTPE. The fluorescence quantum yields （ΦF） of F1-（2,2）-HTPE （ΦF=35.1%） and FI-（1,2）-HTPE （ΦF=26.2%） were found to be higher in solution compared to the near quenching of F 1-TPE （ΦF = 0.1%）. Consequently, this results in weaker AIE-stability of F1-（2,2）-HTPE （αAIE= 1.5） and F1-（1,2）-HTPE （αAIE=1.9） compared to F1-TPE （αAIE=125）, suggesting that four phenyl groups are necessary for efficient AIE-activity of these fluorene bridged arylene vinylene type materials In addition, decreasing the steric hindrance around the arylene vinylene moiety by removal of a phenyl ring is an- other method to decrease the AIE characteristics, in a similar manner to the commonly known ＂phenyl-locking＂. Non-polar triphenylethenes are poorer AlE materials than their tetraphenylethene analogues. Replacing the hydro- gen atom of F1-（2,2）-HTPE with a cyano group affords fluorene end-capped with 2,3,3-triphenylacrylonitrile （F1-TPAN）, which boosts the AIE-effect to αAIE=90.5 and red-shifts the solid-state emission （λem=528 nm） with near quenching in THF solution （ΦF= 0.12%）. X-ray crystallographic analysis of F1-TPAN indicates that the intro- duction of cyano groups can noWe have synthesized a series of fluorene-based fluorophores, in which a central fluorene core has been modified with different peripheral arylene vinylene substituents that are able to activate aggregation-induced emission （AIE） characteristics. 9,9-Dioctylfluorene doubly end-capped at the 2,7-positions with triphenylethene groups, such as 4-（2,2-diphenylvinyl）phenyl （F1-（2,2）-HTPE） and 4-（1,2-dipbenylvinyl）phenyl （F1-（1,2）-HTPE） were synthesized and compared to the tetraphenylethene analogue （F1-TPE）. Both FI-（2,2）-HTPE and F1-（1,2）-HTPE glow with a deep blue fluorescence in THF solution with emission maxima （λem） of 426 and 403 nm, respectively. The λem slightly red-shifts in the solid-state to 458 nm for F 1-（2,2）-HTPE and 437 nm for F 1-（1,2）-HTPE. The fluorescence quantum yields （ΦF） of F1-（2,2）-HTPE （ΦF=35.1%） and FI-（1,2）-HTPE （ΦF=26.2%） were found to be higher in solution compared to the near quenching of F 1-TPE （ΦF = 0.1%）. Consequently, this results in weaker AIE-stability of F1-（2,2）-HTPE （αAIE= 1.5） and F1-（1,2）-HTPE （αAIE=1.9） compared to F1-TPE （αAIE=125）, suggesting that four phenyl groups are necessary for efficient AIE-activity of these fluorene bridged arylene vinylene type materials In addition, decreasing the steric hindrance around the arylene vinylene moiety by removal of a phenyl ring is an- other method to decrease the AIE characteristics, in a similar manner to the commonly known ＂phenyl-locking＂. Non-polar triphenylethenes are poorer AlE materials than their tetraphenylethene analogues. Replacing the hydro- gen atom of F1-（2,2）-HTPE with a cyano group affords fluorene end-capped with 2,3,3-triphenylacrylonitrile （F1-TPAN）, which boosts the AIE-effect to αAIE=90.5 and red-shifts the solid-state emission （λem=528 nm） with near quenching in THF solution （ΦF= 0.12%）. X-ray crystallographic analysis of F1-TPAN indicates that the intro- duction of cyano groups can no

关 键 词：aggregation-induced emission FLUORENE triphenylethene tetraphenylethene 2 3 3-triphenylacrylonitrile 

分 类 号：O484.41[理学—固体物理] TQ221.211[理学—物理]