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meso ‐Cumulenic 2H ‐Corroles from meso ‐Ethynyl‐ 3H ‐corroles
Author(s) -
Ueta Kento,
Naoda Koji,
Ooi Shota,
Tanaka Takayuki,
Osuka Atsuhiro
Publication year - 2017
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201703139
Subject(s) - corrole , chemistry , photochemistry
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 PbO 2 . Both 10 a and 12 b were metalated to form Zn II 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≈1.0×10 5 m −1 cm −1 ) owing to the effective π‐conjugation between the two corrole units through the [5]cumulene bridge.