Synthesis, photophysical and photochemical properties of photoacid generators based on N-hydroxyanthracene-1,9-dicarboxyimide and their application toward modification of silicon surfaces

Mohammed Ikbal; Rakesh Banerjee; Sanghamitra Atta; Dibakar Dhara; Anakuthil Anoop; N D Pradeep Singh

doi:10.1021/jo301367y

Synthesis, photophysical and photochemical properties of photoacid generators based on N-hydroxyanthracene-1,9-dicarboxyimide and their application toward modification of silicon surfaces

J Org Chem. 2012 Dec 7;77(23):10557-67. doi: 10.1021/jo301367y. Epub 2012 Nov 20.

Authors

Mohammed Ikbal¹, Rakesh Banerjee, Sanghamitra Atta, Dibakar Dhara, Anakuthil Anoop, N D Pradeep Singh

Affiliation

¹ Department of Chemistry, Indian Institute of Technology Kharagpur, Kharagpur-721302, India.

PMID: 23140622
DOI: 10.1021/jo301367y

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.