Solar energy driven C-C bond cleavage in a lignin model compound with a D-∏-A organic dye-sensitized photoanode

Abstract

The high bond dissociation energy of C-C s-bonds presents a challenge to chemical conversions in organic synthesis, polymer degradation, and biomass conversion that require chemoselective C-C bond cleavage at room temperature. Dye-sensitized photoelectrochemical cells (DSPECs) incorporating molecular organic dyes could offer a means of using renewable solar energy to drive these types of energetically demanding chemoselective C-C bond cleavage reactions. This study reports the solar light-driven activation of a bicyclic aminoxyl mediator to achieve C-C bond cleavage in the aryl-ether linkage of a lignin model compound (LMC) at room temperature using a donor-p-conjugated bridge-acceptor (D-p-A) organic dye-based DSPEC system. Mesoporous TiO2 photoanode surfaces modified with 5-[4-(diphenylamino)phenyl]thiophene-2-cyanoacrylic acid (DPTC) D-p-A organic dye were investigated along with a bicyclic aminoxyl radical mediator (9-azabicyclo[3,3,1]nonan-3-one-9-oxyl, KABNO) in solution with and without the presence of LMC. Photophysical studies of DPTC with KABNO showed intermolecular energy/electron transfer under 1 sun illumination (100 mW cm(-2)). Under illumination, the D-p-A type DPTC sensitized TiO2 photoanodes facilitate the generation of the reactive oxoammonium species KABNO(+) as a strong oxidizing agent, which is required to drive the oxidative C-C bond cleavage of LMC. The photoelectrochemical oxidative reaction in a complete DSPEC with KABNO afforded C-C bond cleavage products 2-(2-methoxyphenoxy)acrylaldehyde (94%) and 2,6-dimethoxy-1,4-benzoquinone (66%). This process provides a first report utilizing a D-p-A type organic dye in combination with a bicyclic nitroxyl radical mediator for heterogeneous photoelectrolytic oxidative cleavage of C-C s-bonds, modeled on those found in lignin, at room temperature.