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Abstract

The tetramanganese–calcium cluster of the oxygen‐evolving complex of photosystem II adopts electronically and magnetically distinct but interconvertible valence isomeric forms in its first light‐driven oxidized catalytic state, S₂. This bistability is implicated in gating the final catalytic states preceding O−O bond formation, but it is unknown how the biological system enables its emergence and controls its effect. Here we show that the Mn₄CaO₅ cluster in the resting (dark‐stable) S₁ state adopts orientational Jahn–Teller isomeric forms arising from a directional change in electronic configuration of the “dangler” Mn^III ion. The isomers are consistent with available structural data and explain previously unresolved electron paramagnetic resonance spectroscopic observations on the S₁ state. This unique isomerism in the resting state is shown to be the electronic origin of valence isomerism in the S₂ state, establishing a functional role of orientational Jahn–Teller isomerism unprecedented in biological or artificial catalysis.