All-in-One Photoacid Generators with Green/Red-light Responsiveness and Cooperative Functionality

Angew Chem Int Ed Engl. 2025 Jan 24:e202425313. doi: 10.1002/anie.202425313. Online ahead of print.

Abstract

Photoacid generators (PAGs) are invaluable molecular tools that exhibited tremendous potential in emerging interdisciplinary researches of life-science, nanotechnology and smart materials. However, current PAGs are primarily mono-functional in terms of acid generation and rely on UV/deep-blue light excitation, posing a fundamental hurdle to their broader adoption. Developing cooperatively functioned PAGs with long-wavelength light responsiveness presents a formidable challenge due to the absence of suitable molecular scaffolds. Here, we introduce a newly-developed perylene bisimides PAG motif (PBI-PAG) that integrates desired multi-functionality and visible-light photo-reactivity. Taking advantages of characteristic opto-electronic properties of PBI scaffold, PBI-PAGs are capable of quantitative releasing (> 99%) a palette of acids upon green/red light (560-605 nm) excitation. Concurrently, a photo-generated counterpart is functioned as a photo-sensitizer that could perform cooperatively with acid as an anti-metastasis cancer therapy agent. These two processes constitute the first example of a cooperatively functioned PAG operated at substrate-adaptive wavelengths.

Keywords: Cooperative functionality; Perylene bisimides; Photo-acid; Visible-light excitation; photoisomerization.