Hydrogen-bonding dependent nontraditional fluorescence polyphenylallenes: Controlled synthesis and aggregation-induced emission behaviors

Luminescent polymers have been significantly attractive information storage materials, and the development of controlled luminescent polyallenes with nonconventional luminophores through aggregation-induced emission (AIE) is therefore highly desirable. In this study, two kinds of Chol-carbamate and Chol-ester linker polymers have been successfully fabricated by π-allylnickel(II) complexes upon phenylallene monomers. The polymerization of phenylallenes proceeded in a living manner with controlled Mn and low Mw/Mn Chol-carbamate-linked polyphenylallenes with amide spacer were AIE active luminogens, whereas Chol-ester linked polyaphenylllenes showed aggregation‐caused quenching (ACQ) characteristics. The helical conformation of Chol-carbamate-linked polyphenylallenes was revealed to be stabilized by the adjacent repeating units arising from the degree of polymerization. Experimental and theoretical results demonstrated the hydrogen bonding interaction of amide spacer polymers can increase the helical conformation rigidification, which provides the main means to realize AIE. Moreover, circularly polarized luminescence (CPL) with a tunable emission intensity and dissymmetric factor was observed.