Facile Synthesis of Diversified Biisoquinoline-Containing Polymers by Multicomponent C─H Activation/Annulation...

Area of Science:

• Polymer Chemistry
• Organic Synthesis
• Materials Science

Background:

• Biisoquinoline scaffolds are recognized for their unique photophysical properties and axial chirality, making them valuable in various scientific fields.
• The synthesis of functional biisoquinoline-containing polymers (BCPs) has been significantly hindered by synthetic complexities, limiting their widespread application.
• The development of optically active BCPs through asymmetric catalytic polymerization remains an unachieved goal.

Purpose of the Study:

• To develop an efficient and versatile strategy for synthesizing structurally diverse biisoquinoline-containing polymers (BCPs).
• To achieve the construction of optically active BCPs via asymmetric catalytic polymerization.
• To explore the properties and applications of the synthesized BCPs, including their luminescent characteristics and potential in photopatterning.

Main Methods:

• A multicomponent cascade C─H activation/annulation polymerization (CAAP) strategy was employed.
• Readily available benzil derivatives, internal diynes, and ammonium acetate were used as starting materials.
• Rhodium catalysts were utilized for both achiral and asymmetric CAAP reactions, conducted in a one-pot, one-step operation under air.

Main Results:

• A variety of multisubstituted BCPs with high molecular weights (up to 49900 g mol⁻¹) were synthesized in good yields.
• The resulting BCPs demonstrated excellent solubility, good film-forming capabilities, and tunable luminescent properties.
• Optically active BCPs and BCP-metal complexes with stable axially chiral configurations were successfully generated using chiral rhodium catalysts.

Conclusions:

• The developed CAAP strategy provides facile access to diverse BCPs, overcoming previous synthetic limitations.
• The synthesized BCPs possess desirable properties for applications in materials science, particularly in creating high-resolution fluorescent photopatterns.
• This work represents the first successful construction of optically active BCPs via asymmetric catalytic polymerization, opening new avenues for chiral materials development.