Chiral Aggregates of Triphenylamine‐Based Dyes for Depleting the Production of Hydrogen Peroxide in the Photochemical Water‐Splitting Process. Issue 5 (17th April 2019)

• Record Type: Journal Article
• Authors: Adelizzi, Beatrice; Rösch, Andreas T.; van Rijen, Daan J.; Martire, R. Simone; Esiner, Serkan; Lutz, Martin; Palmans, Anja R. A.; Meijer, E. W.
• Is Part Of: Helvetica chimica acta. Volume 102:Issue 5(2019)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2019-04-17
• Subjects: dye-sensitized photoelectrochemical cells -- water splitting -- supramolecular chemistry -- chirality -- chiral induced spin selectivity; Chemistry -- Periodicals; Chemistry, Analytical -- periodicals; Chimie -- Périodiques; 540
• DOI: 10.1002/hlca.201900065
• Languages: English
• ISSNs: 0018-019X

Abstract

Abstract: Recent studies on water‐splitting photoelectrochemical cells (PECs) have demonstrated the intriguing possibility of controlling the spin state in this chemical reaction to form H2 and O2 by exploiting the chirality of organic π ‐conjugated supramolecular polymers. Although this fascinating phenomenon has been disclosed, the chiral supramolecular materials reported thus far are not optimized for acting as efficient photosensitizer for dye‐sensitized PECs. In this work we report on the design, synthesis, and characterization of chiral supramolecular aggregates based on C 3 ‐symmetric triphenylamine‐based dyes that are able to both absorb visible light and control the spin state of the process. Variable temperature‐dependent spectroscopic measurements reveal the assembly process of the dyes and confirm the formation of chiral aggregates, both in solution as well as on solid supports. Photoelectrochemical measurements on TiO2 ‐based anodes validate the advantage of using chiral supramolecular aggregates as photosensitizer displaying higher photocurrent compared to achiral analogues. Moreover, fluorimetric tests for the quantification of the hydrogen peroxide produced, confirm the possibility of controlling the spin of the reaction exerting spin‐selection with chiral supramolecular polymers. These results represent a further step towards the next‐generation of organic‐based water‐splitting solar cells. Abstract :