Synthesis, Photophysical and Photochemical Properties of Photoacid Generators Based on N-Hydroxyanthracene-1,9-dicarboxyimide and Their Application toward Modification of Silicon Surfaces

Abstract

We have introduced a series of nonionic photoacid generators (PAGs) for carboxylic and sulfonic acids based on N-hydroxyanthracene-1,9-dicarboxyimide (HADI). The newly synthesized PAGs exhibited positive solvachromatic emission (λ(max)(hexane) 461 nm, λ(max)(ethanol) 505 nm) as a function of solvent polarity. Irradiation of PAGs in acetonitrile (ACN) using UV light above 410 nm resulted in the cleavage of weak N-O bonds, leading to the generation of carboxylic and sulfonic acids in good quantum and chemical yields. Mechanism for the homolytic N-O bond cleavage for acid generation was supported by time-dependent density functional theory (TD-DFT) calculations. More importantly, using the PAG monomer N-(p-vinylbenzenesulfonyloxy)anthracene-1,9-dicarboxyimide (VBSADI), we have synthesized N-(p-vinylbenzenesulfonyloxy)anthracene-1,9-dicarboxyimide-methyl methacrylate (VBSADI-MMA) and N-(p-vinylbenzenesulfonyloxy)anthracene-1,9-dicarboxyimide-ethyl acrylate (VBSADI-EA) copolymer through atom transfer radical polymerization (ATRP). Finally, we have also developed photoresponsive organosilicon surfaces using the aforementioned polymers.