Hisamune Yutaka, Kim Taeyeon, Nishimura Keiichi, Ishida Masatoshi, Toganoh Motoki, Mori Shigeki, Kim Dongho, Furuta Hiroyuki
Department of Chemistry and Biochemistry, Graduate School of Engineering, and Center for Molecular Systems, Kyushu University, Fukuoka, 819-0395, Japan.
Department of Chemistry, Yonsei University, Seoul, 120-749, Korea.
Chemistry. 2018 Mar 26;24(18):4628-4634. doi: 10.1002/chem.201705516. Epub 2018 Mar 5.
A novel helically twisted π-extended corrorin derivative having two boron dipyrrin (BODIPY) moieties at the periphery, a BODIPY DYEmer (6-BF ) cross-bridged with π-conjugated dipyrrinylidene unit, was synthesized and characterized. The neutral 6-BF is nonfluorescent due to the internal photoinduced charge transfer (CT) character in the excited state as inferred from the femtosecond transient absorption spectroscopy. However, upon protonation, the CT process is suppressed and the species H6-BF becomes near infrared (IR) emissive. With the aid of rigid helical conformations in 6-BF , the helical isomers (P- and M-forms) were resolved and their chiroptical property was investigated. The distinct circular dichroism (CD) spectral changes of the enantiomers were observed in the presence of acids, which demonstrates that 6-BF can be utilized for potential acid-responsive chiroptical materials.
合成并表征了一种新型的螺旋扭曲π-扩展corrorin衍生物，其外围具有两个硼二吡咯（BODIPY）部分，一个BODIPY DYEmer（6-BF）与π共轭二吡咯亚基交叉桥连。飞秒瞬态吸收光谱表明，中性的6-BF由于激发态的内部光致电荷转移（CT）特性而无荧光。然而，质子化后，CT过程受到抑制，物种H6-BF变为近红外（IR）发射。借助6-BF中的刚性螺旋构象，分离出螺旋异构体（P型和M型）并研究了它们的手性光学性质。在酸存在下观察到对映体明显的圆二色性（CD）光谱变化，这表明6-BF可用于潜在的酸响应手性光学材料。
