RESUMO
Dye-sensitized photoelectrochemical cells can enable the production of molecules currently accessible through energetically demanding syntheses. Copper(I)-based dyes represent electronically tunable charge transfer and separation systems. Herein, we report a Cu(I)-bisdiimine donor-chromophore-acceptor dye with an absorbance in the visible part of the solar spectrum composed of a phenothiazine electron donor, and dipyrido[3,2-a:2',3'-c]phenazine electron acceptor. This complex is incorporated onto a zinc oxide nanowire semiconductor surface effectively forming a photoanode that is characterized spectroscopically and electrochemically. We investigate the photo-oxidation of hydroquinone, and the photosensitization of 2,2,6,6-tetramethylpiperidine-1-oxyl and N-hydroxyphthalimide for the oxidation of furfuryl alcohol to furfuraldehyde, resulting in near quantitative conversions, with poor selectivity to the alcohol.
RESUMO
Porphyrins are important molecules widely found in nature in the form of enzyme active sites and visible light absorption units. Recent interest in using these functional molecules as building blocks for the construction of metal-organic frameworks (MOFs) have rapidly increased due to the ease in which the locations of, and the distances between, the porphyrin units can be controlled in these porous crystalline materials. Porphyrin-based MOFs with atomically precise structures provide an ideal platform for the investigation of their structure-function relationships in the solid state without compromising accessibility to the inherent properties of the porphyrin building blocks. This review will provide a historical overview of the development and applications of porphyrin-based MOFs from early studies focused on design and structures, to recent efforts on their utilization in biomimetic catalysis, photocatalysis, electrocatalysis, sensing, and biomedical applications.
