Development of 1‐Hydroxy‐2(1H)‐quinolone‐Based Photoacid Generators and Photoresponsive Polymer Surfaces

Abstract

A new class of carboxylate and sulfonate esters of 1‐hydroxy‐2(1H)‐quinolone has been demonstrated as nonionic photoacid generators (PAGs). Irradiation of carboxylates and sulfonates of 1‐hydroxy‐2(1H)‐quinolone by UV light (λ≥310 nm) resulted in homolysis of weak NO bond leading to efficient generation of carboxylic and sulfonic acids, respectively. The mechanism for the homolytic NO bond cleavage was supported by time‐dependent DFT calculations. Photoresponsive 1‐(p‐styrenesulfonyloxy)‐2‐quinolone–methyl methacrylate (SSQL‐MMA) and 1‐(p‐styrenesulfonyloxy)‐2‐quinolone–lauryl acrylate (SSQL‐LA) copolymers were synthesized from PAG monomer 1‐(p‐styrenesulfonyloxy)‐2‐quinolone, and subsequently controlled surface wettability was demonstrated for the above‐mentioned photoresponsive polymers.

Aryl tosylates as non-ionic photoacid generators (PAGs): photochemistry and applications in cationic photopolymerizations

“…The compounds proposed for this role usually release a sulfonic acid upon photocleavage of a weak N-O bond in iminosulfonates, 4,5 imidosulfonates 5 (Scheme 1a) or related compounds. 6 Such cleavage generates a RSO 3 c radical, which upon reaction with the medium, is able to form a strong sulfonic acid.…”

Facile Synthesis and Properties of 2‐λ5‐Phosphaquinolines and 2‐λ5‐Phosphaquinolin‐2‐ones

“…[16] The imidate structure indicates some π-electron delocalization within the heterocycle, with the C(1)–C(2) double bond length (1.367 Å) intermediate between benzene and an isolated double bond, whereas the same bond in 11j (1.341 Å) is nearly identical to the corresponding bond length in carbostyril (1.343 Å). [17] The azaphosphinine ring in 10j shows only small deviations from planarity (RMSD 0.014 Å). Analysis of crystal structure and computational models (see Supporting Information) indicate that the enhanced stability of 10j to hydrolysis is likely due to co-planarity of pyridine and the azaphosphinine ring, held by a weak hydrogen bond between the hydrogen atom on C(2) and the pyridine nitrogen atom.…”

Facile Synthesis and Properties of 2‐λ5‐Phosphaquinolines and 2‐λ5‐Phosphaquinolin‐2‐ones

“…The PN bond in 10 j (1.565 Å) is much shorter than the amidate PN bond in 11 j (1.635 Å) but is similar to the analogous bond in hexaphenoxycyclotriphosphazene (1.575 Å) 16. The imidate structure indicates some π‐electron delocalization within the heterocycle, with the C(1)C(2) double bond length (1.367 Å) intermediate between that of benzene and an isolated double bond, whereas the same bond in 11 j (1.341 Å) is nearly identical in length to the corresponding bond in carbostyril (1.343 Å) 17. The azaphosphinine ring in 10 j shows only small deviations from planarity (RMSD 0.014 Å).…”