Synthesis,characterization, and photoreaction of photoreactive liquid crystalline block copolyetheresters

Photo-crosslinkable thermotropic liquid crystalline block copolyetheresters with photoreactive hard segment of poly(hexamethylene p-phenylenediacrylate) and soft segment of poly(tetramethylene ether) were synthesized by melt polycondensation from n-butyl-p-phenylenediacrylate, hexamethylene glycol, and poly(tetramethylene ether) glycol (PTMG, M_n = 1000–3000). The influence of molecular weight and composition of PTMG unit on the thermal behavior was determined by differential scanning calorimetry and polarized optical microscopy. All synthesized block copolymers show thermotropic liquid crystalline phase and can photo-crosslink by UV irradiation. Photoreaction of the copolymer thin film was carried out using Hg-UV light and investigated by FT–IR spectroscopy and a dynamic viscoelastic analyzer. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 1849–1855, 1997     

Blue-to-UVB Upconversion,Solvent Sensitization and Challenging Bond Activation Enabled by a Benzene-Based Annihilator

Several energy-demanding photoreactions require harsh UV light from inefficient light sources. The conversion of low-energy visible light to high-energy singlet states via triplet-triplet annihilation upconversion (TTA-UC) could offer a solution for driving such reactions under mild conditions. We present the first annihilator with an emission maximum in the UVB region that, combined with an organic sensitizer, is suitable for blue-to-UVB upconversion. The annihilator singlet was successfully employed as an energy donor in subsequent FRET activations of aliphatic carbonyls. This hitherto unreported UC-FRET reaction sequence was directly monitored using laser spectroscopy and applied to mechanistic irradiation experiments demonstrating the feasibility of Norrish chemistry. Our results provide clear evidence for a novel blue light-driven substrate or solvent activation strategy, which is important in the context of developing more sustainable light-to-chemical energy conversion systems.