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Synthetic complexes provide useful models to study the interplay between the structure and spectroscopy of the different Sn-state intermediates of the oxygen-evolving complex (OEC) of photosystem II (PSII). Complexes containing the MnIV4 core corresponding to the S3 state, the last observable intermediate prior to dioxygen formation, remain very rare. Toward the development of synthetic strategies to stabilize highly oxidized tetranuclear complexes, ligands with increased anion charge were pursued. Herein, we report the synthesis, electr