Prasad Nambiar Anjana, Nag Probal, Mariam Ipe Ruth, Reddy Vennapusa Sivaranjana, Gokulnath Sabapathi
Department of Chemistry, Indian Institute of Science Education and Research, Thiruvananthapuram, Vithura, Maruthamala P.O., Thiruvananthapuram, 695551, India.
Angew Chem Int Ed Engl. 2023 Jul 24;62(30):e202306566. doi: 10.1002/anie.202306566. Epub 2023 Jun 16.
Herein, we report the synthesis of anthracene-containing twisted cyclo[2]dipyrrin 1 by utilizing a non-planar building block, 1,5-dipyrrylanthracene (1,5-DPA). The non-planar nature of the macrocycle enhanced the solubility and helped in structural characterization. Macrocycle 1 adopts a twisted 'figure of eight' conformation stabilized by strong intramolecular H-bonding interactions and exists as a pair of helical enantiomers, as revealed by X-ray crystallographic analysis. More importantly, the sterically locked structure enabled facile optical resolution using chiral HPLC. The (P,P) and (M,M) enantiomers show moderate chiroptical properties, such as absorption dissymmetry factors |g | in the order of 10 , and luminescence dissymmetry factors |g | of 3.8×10 and 2.9×10 at 702 nm, respectively.
在此，我们报道了通过使用非平面结构单元1,5-二吡咯并蒽（1,5-DPA）合成含蒽的扭曲环[2]二吡咯1。大环的非平面性质增强了其溶解性并有助于结构表征。如X射线晶体学分析所示，大环1采用通过强分子内氢键相互作用稳定的扭曲“8字形”构象，并以一对螺旋对映体形式存在。更重要的是，这种空间锁定结构使得使用手性高效液相色谱法进行简便的光学拆分成为可能。（P,P）和（M,M）对映体表现出适度的手性光学性质，例如吸收不对称因子|g|约为10，在702 nm处的发光不对称因子|g|分别为3.8×10和2.9×10。
