氧化还原开关型 20π-, 19π-, 和 18π-电子 5,10,15,20-四芳基-5,15-二氮杂卟啉镍(II)配合物。
Redox-Switchable 20π-, 19π-, and 18π-Electron 5,10,15,20-Tetraaryl-5,15-diazaporphyrinoid Nickel(II) Complexes.
机构信息
Department of Chemistry, Faculty of Science, Niigata University, Nishi-ku, Niigata, 950-2181, Japan.
Department of Chemistry, College of Science, Rikkyo University, Toshima-ku, Tokyo, 171-8501, Japan.
出版信息
Angew Chem Int Ed Engl. 2016 Feb 5;55(6):2235-8. doi: 10.1002/anie.201510734. Epub 2016 Jan 8.
The first examples of air-stable 20π-electron 5,10,15,20-tetraaryl-5,15-diaza-5,15-dihydroporphyrins, their 18π-electron dications, and the 19π-electron radical cation were prepared through metal-templated annulation of nickel(II) bis(5-arylamino-3-chloro-8-mesityldipyrrin) complexes followed by oxidation. The neutral 20π-electron derivatives are antiaromatic and the cationic 18π-electron derivatives are aromatic in terms of the magnetic criterion of aromaticity. The meso N atoms in these diazaporphyrinoids give rise to characteristic redox and optical properties for the compounds that are not typical of isoelectronic 5,10,15,20-tetraarylporphyrins.
首例稳定的空气 20π 电子 5,10,15,20-四芳基-5,15-二氮-5,15-二氢卟啉、它们的 18π 电子二阳离子和 19π 电子自由基阳离子是通过镍（II）双（5-芳基氨基-3-氯-8-均三甲苯基二吡咯）配合物的金属模板环化，然后氧化制备的。根据芳香性的磁判据，中性 20π 电子衍生物是反芳香的，而阳离子 18π 电子衍生物是芳香的。这些二氮杂卟啉化合物中的中位 N 原子赋予了化合物特征的氧化还原和光学性质，这与等电子的 5,10,15,20-四芳基卟啉不同。
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