Non-planar [n]cyclo-1,8-carbazolylenes (n=3,4,6) and [3]cyclo-1,8-carbazolylenyl B, P, PO, SiPh complexes
Non-planar [n]cyclo-1,8-carbazolylenes (n=3,4,6) and [3]cyclo-1,8-carbazolylenyl B, P, PO, SiPh complexes
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非平面 [n] 环-1,8-咔唑基 (n=3,4,6) 和 [3]环-1,8-咔唑基 B、P、PO、SiPh 配合物
DOI：
10.1002/chem.201702853
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发表时间：
2017
期刊：
影响因子：
--
通讯作者：
Shuhei Higashibayashi
中科院分区：
文献类型：
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作者：
Koji Yamamoto;Palash Pandit;Shuhei Higashibayashi
创建了一个新的由咔唑组成的非平面杂环分子家族。以1，8-二溴咔唑为原料，通过Ni 0催化的一次环齐聚反应，合成了碗状环二聚体、片状环三聚体、双德克尔环状环四聚体和环六聚体，命名为[n]环1，8-咔唑亚基（n= 3，4，6）. [3]发现环-1，8-亚咔唑基作为杂原子（B，P，Si）的三价三齿配体，产生片状配合物。硼衍生物作为一个刘易斯酸，和四配位的配合物显示出前所未有的红移的吸收和发射光谱的配位。[3]环-1，8-咔唑烯的合成方法、畸变的C2或C1对称形状、三价三齿配位能力和引入的杂原子种类、电子结构、物理性质和刘易斯酸性都与相关的亚卟啉/亚酞菁不同。
A new family of non‐planar heterocyclic molecules consisting of carbazoles was created. A bowl‐shaped cyclodimer, a flake‐shaped cyclotrimer, a double‐decker‐ring‐shaped cyclotetramer and a cyclohexamer were synthesized by Ni0‐mediated one‐shot cyclo‐oligomerization of 1,8‐dibromocarbazole, and were named [n]cyclo‐1,8‐carbazolylenes (n=3,4,6). [3]Cyclo‐1,8‐carbazolylene was found to act as a trivalent tridentate ligand for heteroatoms (B, P, Si), giving flake‐shaped complexes. The boron derivative acted as a Lewis acid, and the tetra‐coordinated complexes showed an unprecedented red‐shift of absorption and emission spectra by the coordination. The synthetic method, the distortedC2orC1symmetric shape, the trivalent tridentate coordination ability and the kinds of introduced heteroatoms of [3]cyclo‐1,8‐carbazolylenes, the electronic structure, the photophysical property, and the Lewis acidity were distinct from those of related subporphyrins/subphthalocyanines.