Rhodium-Catalyzed Polycyclotrimerization of Diphenylpropiolates: A Facile Strategy toward Ester-Functionalized Hyperbranched Polyarylenes

作者：Fang, Huikang; Huo, Xiaoyang; Wang, Lu; Si, Han; Li, Hongkun^*; Qin, Anjun; Tang, Ben Zhong; Li, Yongfang

来源：Macromolecules, 2022, 55(7): 2456-2462.

DOI：10.1021/acs.macromol.1c02618

• AGGREGATION-INDUCED EMISSION
• POLYMERS
• POLYMERIZATION
• POLYPHENYLENE
• THIOL
• AIE

Alkyne polycyclotrimerizations have become efficient synthetic tools for constructing hyperbranched polypheny-lenes. However, the polycyclotrimerization reactions of internalalkynes are rarely reported. Herein, we present thefirst example ofRhCl3-catalyzed polycyclotrimerization of activated internal diynesto prepare hyperbranched polymers. The polymerization reactionsof diphenylpropiolates (1a-c) were performed in toluene underreflux in the presence of RhCl3middot3H2O andN,N-diisopropylethyl-amine (DIPEA), affording soluble hyperbranched poly-(triphenylbenzoate)s (hb-PTPBs),hb-P1a-c, with high molecularweights (up to 187000) and high regioregularities (fraction of 1,2,4-triphenylbenzoate isomer up to 88.2%) in satisfactory yields. The degree of branching ofhb-P1awas determined to be 0.73. The resultan thb-PTPBs are thermally stable, with 5% weight losstemperatures higher than 330 degrees C. The hb-PTPBs are weakly emissive in their dilute solutions but become intensively emissive upon aggregate formation, showing aggregation-induced emission features

• 单位
  苏州大学