Preparation of 9,10-Diarylphenanthrene Derivative and Its Application in Full Color Emitters Synthesis  

作　　者：ZHAO Wenkai WANG Zhiming LI Xueying ZHANG Dongdong ZHANG Xiaojuan LU Ping 

机构地区：[1]School of Petrochemical Engineering, Shenyang University of Technology, Liaoyang 111003, P. R. China [2]State Key Laboratory of Supramoleeular Structure and Materials, Jilin University, Changchun 130012, P. R. China [3]Shenzhen Research Institute, Hong Kong University of Science & Technology, Shenzhen 518057, P. R. China

出　　处：《Chemical Research in Chinese Universities》2017年第4期574-580,共7页高等学校化学研究（英文版）

基　　金：Supported by the National Natural Science Foundation of China（No.51673118）, the Natural Science Fund of Guangdong Province, China（No.2014A030313659） and the Science and Technology Plan of Shenzhen City, China（No.JCYC20160428150- 429072）.

摘　　要：As a building block with high photo- and thermo-stability, phenanthrene plays an important role in the preparation of blue（or deep-blue） and full color fluorescence materials. However, some critical issues must be addressed before its full potential can be realised, such as its tedious and low-yield modification processes and the red-shift effect in its aggregated state. In this work, the inexpensive raw material 9,10-phenanthrenequinone（PQ） was chosen as the preparatory functional phenanthrene block. After modifying PQ via halo-substituted, nucleophilic and rearrangement reactions with high yields, the corresponding monomers featured high reactivity and solubility. Com- pared with classical synthetic approaches for similar phenanthrene-based derivatives, the low efficiency ring-closed reaction and hazardous lithium-injection operation can be omitted using this approach. This new building block demonstrates a clear steric effect following the introduction of peripheral phenyl and alkoxy groups; moreover~ stacking in the aggregated state is avoided, which benefits controlling the bandgap and maintaining blue emission as either an emitter or a donor. By changing the central building block in three oligomers, emission of the three primary colors was achieved in solution and film via the conjugated increment and charge-transform effect. This work provides a method of modifying phenanthrene by a simple and efficient synthesis route with inhibition of solid-state aggregation and offers an effective strategy to further develop functional phenanthrene-based building blocks.As a building block with high photo- and thermo-stability, phenanthrene plays an important role in the preparation of blue（or deep-blue） and full color fluorescence materials. However, some critical issues must be addressed before its full potential can be realised, such as its tedious and low-yield modification processes and the red-shift effect in its aggregated state. In this work, the inexpensive raw material 9,10-phenanthrenequinone（PQ） was chosen as the preparatory functional phenanthrene block. After modifying PQ via halo-substituted, nucleophilic and rearrangement reactions with high yields, the corresponding monomers featured high reactivity and solubility. Com- pared with classical synthetic approaches for similar phenanthrene-based derivatives, the low efficiency ring-closed reaction and hazardous lithium-injection operation can be omitted using this approach. This new building block demonstrates a clear steric effect following the introduction of peripheral phenyl and alkoxy groups; moreover~ stacking in the aggregated state is avoided, which benefits controlling the bandgap and maintaining blue emission as either an emitter or a donor. By changing the central building block in three oligomers, emission of the three primary colors was achieved in solution and film via the conjugated increment and charge-transform effect. This work provides a method of modifying phenanthrene by a simple and efficient synthesis route with inhibition of solid-state aggregation and offers an effective strategy to further develop functional phenanthrene-based building blocks.

关 键 词：PHENANTHRENE FUNCTIONALIZATION AGGREGATION FLUORESCENCE Three primary colors emission 

分 类 号：TQ231.11[化学工程—有机化工] O636.1[理学—高分子化学]