基于 2,7,12,17-四（对硼酸频哪醇酯）镍卟啉的四重桥联非偏移面对面卟啉二聚体和十字形五聚卟啉带。
A Quadruply Bridged Non-Offset Face-to-Face Porphyrin Dimer and Cross-Shaped Pentameric Porphyrin Tapes Based on 2,7,12,17-Tetrakis(pinacolatoboryl) Ni Porphyrin.
机构信息
Key Laboratory of Chemical Biology and Traditional Chinese Medicine, Ministry of Educational 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, Changsha, 410081, China.
Division of Materials Science, Nara Institute of Science and Technology (NAIST), 8916-5 Takayama-cho, Ikoma, 630-0192, Japan.
出版信息
Angew Chem Int Ed Engl. 2023 Mar 20;62(13):e202300260. doi: 10.1002/anie.202300260. Epub 2023 Feb 20.
2,7,12,17-Tetrakis(pinacolatoboryl) Ni porphyrin 5 Ni was synthesized in 75 % yield by Ir-catalyzed borylation of porphine followed by Ni metalation and has been demonstrated to be a useful synthon, giving 2,7,12,17-tetraaryated Ni porphyrins 6 a-d, peripherally octaarylated Ni porphyrins 8 a-d, quadruply bridged face-to-face non-offset Ni -porphyrin dimer 12, and cross-shaped β-meso singly linked porphyrin pentamers and nonamers. Oxidation of cross-shaped β-meso singly linked porphyrin pentamers 14 Ni and 14 Zn gave fused pentameric tapes 15 Ni and 15 Zn. The structures of 12, 14 Zn, and 15 Ni have been revealed by X-ray diffraction analysis. Optical separation of 12 has been accomplished, showing a bisignate coupling pattern for exciton-coupled blue-shifted Soret band. Pentameric porphyrin tape 15 Zn exhibits a red-shifted absorption band at 1156 nm and seven reversible redox waves.
2,7,12,17-四(联硼酸频那醇酯)Ni 卟啉 5Ni 通过卟啉的 Ir 催化硼酸化反应合成，产率为 75%，然后进行 Ni 金属化，已被证明是一种有用的合成子，可得到 2,7,12,17-四芳基 Ni 卟啉 6a-d、外围八芳基 Ni 卟啉 8a-d、面面对面四重桥联非偏移 Ni-卟啉二聚体 12 和十字形β-中位单键连接卟啉五聚体和九聚体。十字形β-中位单键连接卟啉五聚体 14Ni 和 14Zn 的氧化得到了稠合五聚体带 15Ni 和 15Zn。通过 X 射线衍射分析揭示了 12、14Zn 和 15Ni 的结构。12 已通过光学分离，显示出用于激子耦合蓝移 Soret 带的双信号耦合模式。五聚体卟啉带 15Zn 在 1156nm 处表现出红移吸收带和七个可逆氧化还原波。
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