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Phthalocyanine as a Bioinspired Model for Chlorophyll f ‐Containing Photosystem II Drives Photosynthesis into the Far‐Red Region
Author(s) -
FollanaBerná Jorge,
Farran Rajaa,
Leibl Winfried,
Quaranta Annamaria,
SastreSantos Ángela,
Aukauloo Ally
Publication year - 2021
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202101051
Subject(s) - photochemistry , chemistry , intramolecular force , photosystem ii , electron transfer , artificial photosynthesis , photosynthesis , p680 , p700 , photosystem i , electron acceptor , stereochemistry , photocatalysis , catalysis , organic chemistry , biochemistry
Abstract The textbook explanation that P 680 pigments are the red limit to drive oxygenic photosynthesis must be reconsidered by the recent discovery that chlorophyll f (Chl f )‐containing Photosystem II (PSII) absorbing at 727 nm can drive water oxidation. Two different families of unsymmetrically substituted Zn phthalocyanines (Pc) absorbing in the 700–800 nm spectral window and containing a fused imidazole‐phenyl substituent or a fused imidazole‐hydroxyphenyl group have been synthetized and characterized as a bioinspired model of the Chl f /Tyrosine Z /Histidine 190 cofactors of PSII. Transient absorption studies in the presence of an electron acceptor and irradiating in the far‐red region evidenced an intramolecular electron transfer process. Visible and FT‐IR signatures indicate the formation of a hydrogen‐bonded phenoxyl radical in ZnPc II‐OH. This study sets the foundation for the utilization of a broader spectral window for multi‐electronic catalytic processes with one of the most robust and efficient dyes.