Synthesis and photophysical and electrochemical study of tyrosine covalently linked to high-valent copper(III) and manganese(IV) complexes

• As bio-inspired chemical model of the oxygen-evolving complex (OEC) in photosystem II, a new tyrosine-modified corrole ligand 3 and its high-valent copper and manganese complexes 3a and 3b were synthesized and characterized. The copper complexes 1a and 2a of corrole 1 and 2 were also prepared for comparison. The emission property indicates that the emission of ligands 2 and 3 is located at 670 nm, but no emission is observed for their metal complexes due to its suppression by the metal center. The electrochemical study shows that 3a might dimerize at the first two reversible oxidations, a behavior which was not observed in the case of In and 2a. ne corrolato manganese(IV) complex 3b shows one reversible reduction and one quasireversible oxidation at -0.17 and 0.77 V vs. Ag/Ag+, respectively.

Nyckelord

photosynthetic oxygen evolution

coupled electron-transfer

photosystem-ii

water-oxidation

resonance raman

compound-i

corroles

catalysts

peroxidase

absorption

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