Synthesis, Structural Characterization, and Reductive Cleavage of an Oxygen‐Containing Naphthyl Macrocycle

A small macrocycle comprising ether‐bridged naphthyl units was prepared in a two‐step synthesis. Single‐crystal X‐ray diffraction of two polymorphs are reported, one of which showed multiple C−H⋅⋅⋅πnaphthyl interactions of a solvent molecule in the cavity of the macrocycle. Chemical reduction led to C−O bond cleavages accompanied by a Z/E isomerization. The resulting twofold negatively charged (E)‐1,2‐bis(2‐naphthyl)ethylene fragment was isolated as its potassium salts. Electronic characterization revealed a singlet ground state, and a marked distortion of the central ethylene unit was observed upon electron uptake. A naphthyl‐ether based macrocycle suffers multiple C−O cleavages under chemical reduction. The structures of the macrocycle and the resulting negatively charged fragment are analyzed in detail including single‐crystal X‐ray diffraction studies.