Affiliation:
1. Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research (Ministry of Education of China) Key Laboratory of the Assembly and Application of Organic Functional molecules of Hunan Province College of Chemistry and Chemical Engineering Hunan Normal University 410081 Changsha China
2. Department of Chemistry Graduate School of Science, Kyoto University Sakyo-ku 606-8502 Kyoto Japan
Abstract
AbstractSingly‐linked aromatic [22]smaragdyrin BF2 complex dimer was synthesized by the reductive coupling of 16‐brominated [22]smaragdyrin BF2 complex, which was oxidized to a stable diradical with PbO2. As the first example of fused smaragdyrin dimer, a fused [22]smaragdyrin BF2 complex dimer was synthesized by the oxidation of a CuCl‐BF2 complex dimer with FeCl3 and subsequent reduction with NaBH4. After removal of the BF2 group, the singly‐linked and fused aromatic dimers were oxidized to the corresponding antiaromatic [20]smaragdyrin free base dimers. The first oxidation and reduction potentials of these dimers are split depending upon the intramolecular electronic interactions, which are larger for the fused dimers. Despite the large electronic interactions, the aromatic and antiaromatic characters are well preserved in the fused dimers.
Funder
National Natural Science Foundation of China