N,O-Bidentated difluoroboron complexes based on pyridine-ester enolates:Facile synthesis,post-complexation modification,optical properties,and applications  

作　　者：Chaochao Jin Kai Li Jiongpei Zhang Zhihua Wang Jiajing Tan 

机构地区：[1]College of Chemistry,Beijing University of Chemical Technology(BUCT),Beijing 100029,China [2]College of Materials Science and Engineering,Shenzhen University,Shenzhen 518055,China

出　　处：《Chinese Chemical Letters》2024年第9期169-174,共6页中国化学快报（英文版）

基　　金：grateful for the support by the National Natural Science Foundation of China(Nos.21702013,22271010)。

摘　　要：An array of pyridine-ester enolate based organoboron complexes has been designed and synthesized via a one-pot cascade of Pd-catalyzedα-arylation and BF2complexation.The rapid structure-activity relationship(SAR)studies indicated that unsymmetrical N,O-chelated BF2complexes were highly fluorescent in solid state,and exhibited large Stokes shifts,excellent photostability,along with insensitivity to p H.Theα-aryl group could not only modulate the electronic effect but also inhibit the intermolecularπ-πstacking to promote the aggregation-induced emission(AIE)effect.DFT calculations and experiments identified that the intramolecular charge transfer properties of these N,O-chelates could be switched by the modification of substituents,resulting tunable fluorescence wavelengths.Furthermore,post-complexation modification was accomplished,including Suzuki-Miyaura cross-coupling,Buchwald-Hartwig amination,oxidative cleavage,along with a unique triple substitution reaction involving propargyl Grignard reagents.The exemplificative application of dimethylamine substituted boron complex as a reversible acidic vapor sensor was also demonstrated.

关 键 词：N O-Bidentate BF2 complexes Aggregation-induced emission Large Stokes shift Post-complexation modification Reversible acidic vapor sensor 

分 类 号：O641.4[理学—物理化学]