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

摘要

We have introduced a series of nonionic photoacidngenerators (PAGs) for carboxylic and sulfonic acids based on Nhydroxyanthracene-n1,9-dicarboxyimide (HADI). The newly synthesizednPAGs exhibited positive solvachromatic emission (λmax(hexane) 461 nm,nλmax(ethanol) 505 nm) as a function of solvent polarity. Irradiation of PAGsnin acetonitrile (ACN) using UV light above 410 nm resulted in the cleavagenof weak N−O bonds, leading to the generation of carboxylic and sulfonicnacids in good quantum and chemical yields. Mechanism for the homolyticnN−O bond cleavage for acid generation was supported by time-dependentndensity functional theory (TD-DFT) calculations. More importantly, usingnthe PAG monomer N-(p-vinylbenzenesulfonyloxy)anthracene-1,9-dicarboxyimiden(VBSADI), we have synthesized N-(p-vinylbenzenesulfonyloxy)-nanthracene-1,9-dicarboxyimide−methyl methacrylate (VBSADI-MMA) andnN-(p-vinylbenzenesulfonyloxy)anthracene-1,9-dicarboxyimide−ethyl acrylate (VBSADI-EA) copolymer through atom transfernradical polymerization (ATRP). Finally, we have also developed photoresponsive organosilicon surfaces using thenaforementioned polymers.