When heated, bis-Cu(II) octaphyrin(1.1.1.1.1.1.1.1) is quantitatively split into two Cu(II) porphyrins both in solution and film states, which is accompanied by large absorption spectral changes.
A benzopyrane-fused [28]hexaphyrin, 2, was prepared by simple heating of [26]hexaphyrin 1 in acetic acid. Fused [28]hexaphyrin 2 features a molecular twist, a distinct diatropic ring current, a large HOMA value, a large negative NICS value, and a large two-photon absorption (TPA) cross section even at room temperature, all of which support the Möbius aromaticity of 2. To the best of our knowledge, 2 is the first macrocycle that acquires distinct Möbius aromaticity without any assistance from metal coordination, temperature control, or protonation.
Beta-tetraphenyl meso-hexakis(pentafluorophenyl) substituted [26]hexaphyrin is conformationally flexible between rectangular and figure-of-eight shapes and its two-electron reduced [28]hexaphyrin takes figure-of-eight conformations, which are changed, upon protonation, to twisted conformations with distinct Möbius aromaticity.
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