Abstract: | Alkynyl‐substituted 3H‐corrole 9 a was converted to [3]cumulenic 2H‐corrole 10 a by treatment with trimethylsilyl chloride (TMSCl), and 1,3‐butadiyne‐bridged 3H‐corrole dimer 11 b was transformed into [5]cumulene‐bridged 2H‐corrole dimer 12 b by oxidation with PbO2. Both 10 a and 12 b were metalated to form ZnII complexes 10 a‐Zn and 12 b‐Zn . The structures of 10 a‐Zn and 12 b‐Zn show planar conformations with bond‐length alternations that are analogous to those of tetraaryl [n]cumulenes. The cumulenic corrole dimers 12 b and 12 b‐Zn display large NIR absorption bands in the range of 700–1400 nm (maximum ϵ≈1.0×105 m −1 cm−1) owing to the effective π‐conjugation between the two corrole units through the [5]cumulene bridge. |