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Three distinct conformational structures of carbaoctaphyrins were prepared by incorporating bis‐4,4'‐biphenyl units in the macrocyclic core. The free‐base form adopts a figure‐eight conformation, whereas the protonation triggers a conformational change with a pyrrole ring inversion and acquires an open‐framework structure. The insertion of bis‐RhI metal ion in the macrocyclic core affords a singly...
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