Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto, 606-8502, Japan.
Spectroscopy Laboratory of Functional π-Electronic Systems and Department of Chemistry, Yonsei University, 50, Yonsei-ro, Seodaemun-gu, Seoul, 03722, Korea.
Chemistry. 2018 Jun 12;24(33):8306-8310. doi: 10.1002/chem.201801576. Epub 2018 May 15.
Diarylamine-fused subporphyrins 1 a and 1 b were synthesized from β,β-diiodo-meso-chloro subporphyrin 2 through a one-pot procedure involving nucleophilic aromatic substitution and S 1-type intramolecular fusion reaction as the first example of meso-nitrogen-embedded subporphyrin. While non-fused counterparts 3 b and 4 b display effective fluorescence quenching due to twisted intramolecular charge transfer (TICT) in CH Cl at room temperature, 1 b emits fluorescence with Φ =0.18 under the same conditions, because conformational twisting is not allowed due to the fused structure. In addition, the oxidative titration with tris(4-bromophenyl)ammoniumyl hexachloroantimonate gave cation radical 7 for 1 a and cation radical and dication for 1 b. Actually, cation radical 7 was isolated through separation over silica gel column but was found to slowly decompose in concentrated solutions.
二芳胺并-sub 卟啉 1a 和 1b 是通过一锅法从β,β-二碘-meso-氯-sub 卟啉 2 合成的，其中涉及亲核芳香取代和 S1 型分子内融合反应，这是首例嵌入亚氮的 meso-氮-sub 卟啉。虽然非融合的对应物 3b 和 4b 在室温下的 CHCl3 中由于扭曲的分子内电荷转移（TICT）而显示出有效的荧光猝灭，但在相同条件下，1b 发出的荧光的 Φ =0.18，因为融合结构不允许构象扭曲。此外，用三（4-溴苯基）铵六氯锑酸盐进行氧化滴定，得到了 1a 的自由基阳离子 7 和 1b 的自由基阳离子和二阳离子。实际上，自由基阳离子 7 通过硅胶柱分离得到，但在浓溶液中发现其会缓慢分解。
