Ooi Shota, Ueta Kento, Tanaka Takayuki, Osuka Atsuhiro
Department of Chemistry, Graduate School of Science, Kyoto University, Kitashirakawa Oiwake-cho, Sakyo-ku, Japan.
Chempluschem. 2019 Jun;84(6):578-588. doi: 10.1002/cplu.201800570. Epub 2019 Jan 3.
Direct covalent connections of porphyrinoids have been demonstrated as an effective way to expand their π-electronic networks and perturb their optical and electrochemical properties. Covalent connections are also useful for studies on the precise electronic interaction between two porphyrinoid units. However, the chemistry of covalently linked corrole oligomers lags far behind that of the porphyrin counterparts in spite of the importance of corrole as a ring-contracted porphyrinoid. The lower symmetry of corroles naturally leads to many possible corrole dimers, which have been found to display different optical and electrochemical properties depending on the linking position. In this review, we summarize the synthesis, structures, and properties of corrole oligomers such as singly linked oligomers and fused dimers as well as their metal complexes with a particular focus on their linking position dependent electronic properties.
卟啉类化合物的直接共价连接已被证明是扩展其π电子网络并扰动其光学和电化学性质的有效方法。共价连接对于研究两个卟啉类单元之间精确的电子相互作用也很有用。然而,尽管corrole作为一种环收缩的卟啉类化合物很重要,但共价连接的corrole低聚物的化学研究仍远远落后于卟啉类化合物。corrole较低的对称性自然导致许多可能的corrole二聚体,已发现这些二聚体根据连接位置显示出不同的光学和电化学性质。在本综述中,我们总结了corrole低聚物(如单链低聚物和稠合二聚体)及其金属配合物的合成、结构和性质,特别关注其与连接位置相关的电子性质。