Chiral Conjugated Corrals

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• 作者：Melissa Ball ; Brandon Fowler ; Panpan Li ; Leo A. Joyce ; Fang Li ; Taifeng Liu ; Daniel Paley ; Yu Zhong ; Hexing Li ; Shengxiong Xiao ; Fay Ng ; Michael L. Steigerwald ; Colin Nuckolls
• 刊名：Journal of the American Chemical Society
• 出版年：2015
• 出版时间：August 12, 2015
• 年：2015
• 卷：137
• 期：31
• 页码：9982-9987
• 全文大小：459K
• ISSN：1520-5126

文摘

We present here a new design motif for strained, conjugated macrocycles that incorporates two different aromatics into the cycle with an 鈭扐鈥揃鈥揂鈥揃鈥?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 蟺-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 鈥渋ntramolecular somersault鈥?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.