Chiral Conjugated Corrals

• Published in: Journal of the American Chemical Society 2015-08, Vol.137 (31), p.9982-9987
• Main Authors: Ball, Melissa, Fowler, Brandon, Li, Panpan, Joyce, Leo A, Li, Fang, Liu, Taifeng, Paley, Daniel, Zhong, Yu, Li, Hexing, Xiao, Shengxiong, Ng, Fay, Steigerwald, Michael L, Nuckolls, Colin
• Format: Article
• Language: English
• Subjects: Drug Design; Macrocyclic Compounds - chemistry; Models, Molecular; Molecular Conformation; Stereoisomerism; Stress, Mechanical
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/jacs.5b05698

We present here a new design motif for strained, conjugated macrocycles that incorporates two different aromatics into the cycle with an −A–B–A–B– pattern. In this study, we demonstrate the concept by alternating electron donors and acceptors in a conjugated cycle. The donor is a bithiophene, and the acceptor is a perylene diimide derivative. The macrocycle formed has a persistent elliptiform cavity that is lined with the sulfur atoms of the thiophenes and the π-faces of the perylene diimide. Due to the linkage of the perylene diimide subunits, the macrocycles exist in both chiral and achiral forms. We separate the three stereoisomers using chiral high-performance liquid chromatography and study their interconversion. The mechanism for interconversion involves an “intramolecular somersault” in which one of the PDIs rotates around its transverse axis, thereby moving one of its diimide heads through the plane of the cavity. These unusual macrocycles are black in color with an absorption spectrum that spans the visible range. Density functional theory calculations reveal a photoinduced electron transfer from the bithiophene to the perylene diimide.