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, Seoul, 120-749, Korea.
Angew Chem Int Ed Engl. 2017 Sep 25;56(40):12317-12321. doi: 10.1002/anie.201707123. Epub 2017 Aug 23.
A meso-meso β-β β-β triply linked subporphyrin dimer 6 was synthesized by stepwise reductive elimination of β-to-β doubly Pt -bridged subporphyrin dimer 9. Dimer 6 was characterized by spectroscopic and electrochemical measurements, theoretical calculations, and picosecond time-resolved transient absorption spectroscopy. X-ray diffraction analysis reveals that 6 has a bowl-shaped structure with a positive Gaussian curvature. Despite the curved structure, 6 exhibits a remarkably red-shifted absorption band at 942 nm and a small electrochemical HOMO-LUMO gap (1.35 eV), indicating an effectively conjugated π-electronic network.
通过β-至-β 双 Pt 桥联亚卟啉二聚体 9 的逐步还原消除反应，合成了间-间 β-β β-β 三重键联的亚卟啉二聚体 6。通过光谱和电化学测量、理论计算和皮秒时间分辨瞬态吸收光谱对二聚体 6 进行了表征。X 射线衍射分析表明，6 具有碗状结构，具有正高斯曲率。尽管结构弯曲，6 在 942nm 处表现出显著红移的吸收带和较小的电化学 HOMO-LUMO 能隙（1.35eV），表明其具有有效的共轭 π 电子网络。
