In water-oxidizing photosynthetic organisms, light absorption generates a powerfully oxidizing chlorophyll complex (P680(•+)) in the photosystem II reaction centre. This is reduced via an electron transfer pathway from the manganese-containing water-oxidizing catalyst, which includes an electron transfer relay comprising a tyrosine (Tyr)-histidine (His) pair that features a hydrogen bond between a phenol group and an imidazole group. By rapidly reducing P680(•+), the relay is thought to mitigate recombination reactions, thereby ensuring a high quantum yield of water oxidation. Here, we show that an artificial reaction centre that features a benzimidazole-phenol model of the Tyr-His pair mimics both the short-internal hydrogen bond in photosystem II and, using electron paramagnetic resonance spectroscopy, the thermal relaxation that accompanies proton-coupled electron transfer. Although this artificial system is much less complex than the natural one, theory suggests that it captures the essential features that are important in the function of the relay.
Recent advancements in quantum sensing have sparked transformative
detection technologies with high sensitivity, precision, and spatial
resolution. Owing to their atomic-level tunability, molecular qubits
and ensembles thereof are promising candidates for sensing chemical
analytes. Here, we show quantum sensing of lithium ions in solution
at room temperature with an ensemble of organic radicals integrated
in a microporous metal–organic framework (MOF). The organic
radicals exhibit electron spin coherence and microwave addressability
at room temperature, thus behaving as qubits. The high surface area
of the MOF promotes accessibility of the guest analytes to the organic
qubits, enabling unambiguous identification of lithium ions and quantitative
measurement of their concentration through relaxometric and hyperfine
spectroscopic methods based on electron paramagnetic resonance (EPR)
spectroscopy. The sensing principle presented in this work is applicable
to other metal ions with nonzero nuclear spin.
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