The Role of Electron-Donating Subunits in Cross-Linked BODIPY Polymer Films

Abstract

A new method for synthesizing cross-linked 4,4-difluoro-4-bora-3a,4a-diaza-s-indacenes (BODIPYs) using a radical-based thiol-ene click reaction is developed. This method is simple, efficient, and cost-effective, and it produces polymers with unique optical, electrochemical, and surface morphology properties. Significant blue shifts in absorption and photoinduced electron transfer in emissions are observed in the cross-linked BODIPY thin films. Cross-linking also leads to the restriction of conjugation, which results in the breakage of the terminal vinyl group, an increase in the oxidation potential, and a slight upshift in the HOMO position. As a result, the electrochemical band gap is widened from 1.88 to 1.94 eV for polymer bearing N,N-dimethylamino-BODIPY and from 1.97 to 2.02 eV for polymer bearing N,N-diphenylamino-BODIPY moieties. Monomer thin films form planar surfaces due to crystallinity, while amorphous cross-linked BODIPY polymers form more rough surfaces. Additionally, photopatterning on the film surface is successfully performed using different patterned masks. This new method for synthesizing cross-linked BODIPYs has the potential to be used in a variety of applications, including organic electronics, bioimaging, and photocatalysis. © 2023 The Authors. Macromolecular Rapid Communications published by Wiley-VCH GmbH.