title: Chiral Conjugated Corrals.
abstract: 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.
authors.affiliation: †Department of Chemistry, Columbia University, New York, New York 10027, United States.
authors.forename: Melissa
authors.initials: M
authors.lastname: Ball
authors.affiliation: †Department of Chemistry, Columbia University, New York, New York 10027, United States.
authors.forename: Brandon
authors.initials: B
authors.lastname: Fowler
authors.affiliation: ‡The Education Ministry Key Lab of Resource Chemistry, Shanghai Key Laboratory of Rare Earth Functional Materials, Optoelectronic Nano Materials and Devices Institute, Department of Chemistry, Shanghai Normal University, Shanghai, China 200234.|†Department of Chemistry, Columbia University, New York, New York 10027, United States.
authors.forename: Panpan
authors.initials: P
authors.lastname: Li
authors.affiliation: §Process and Analytical Chemistry, Merck Research Laboratories, Rahway, New Jersey 07065, United States.
authors.forename: Leo A
authors.initials: LA
authors.lastname: Joyce
authors.affiliation: ‡The Education Ministry Key Lab of Resource Chemistry, Shanghai Key Laboratory of Rare Earth Functional Materials, Optoelectronic Nano Materials and Devices Institute, Department of Chemistry, Shanghai Normal University, Shanghai, China 200234.
authors.forename: Fang
authors.initials: F
authors.lastname: Li
authors.affiliation: ‡The Education Ministry Key Lab of Resource Chemistry, Shanghai Key Laboratory of Rare Earth Functional Materials, Optoelectronic Nano Materials and Devices Institute, Department of Chemistry, Shanghai Normal University, Shanghai, China 200234.
authors.forename: Taifeng
authors.initials: T
authors.lastname: Liu
authors.affiliation: †Department of Chemistry, Columbia University, New York, New York 10027, United States.
authors.forename: Daniel
authors.initials: D
authors.lastname: Paley
authors.affiliation: †Department of Chemistry, Columbia University, New York, New York 10027, United States.
authors.forename: Yu
authors.initials: Y
authors.lastname: Zhong
authors.affiliation: ‡The Education Ministry Key Lab of Resource Chemistry, Shanghai Key Laboratory of Rare Earth Functional Materials, Optoelectronic Nano Materials and Devices Institute, Department of Chemistry, Shanghai Normal University, Shanghai, China 200234.
authors.forename: Hexing
authors.initials: H
authors.lastname: Li
authors.affiliation: ‡The Education Ministry Key Lab of Resource Chemistry, Shanghai Key Laboratory of Rare Earth Functional Materials, Optoelectronic Nano Materials and Devices Institute, Department of Chemistry, Shanghai Normal University, Shanghai, China 200234.
authors.forename: Shengxiong
authors.initials: S
authors.lastname: Xiao
authors.affiliation: †Department of Chemistry, Columbia University, New York, New York 10027, United States.
authors.forename: Fay
authors.initials: F
authors.lastname: Ng
authors.affiliation: †Department of Chemistry, Columbia University, New York, New York 10027, United States.
authors.forename: Michael L
authors.initials: ML
authors.lastname: Steigerwald
authors.affiliation: ‡The Education Ministry Key Lab of Resource Chemistry, Shanghai Key Laboratory of Rare Earth Functional Materials, Optoelectronic Nano Materials and Devices Institute, Department of Chemistry, Shanghai Normal University, Shanghai, China 200234.|†Department of Chemistry, Columbia University, New York, New York 10027, United States.
authors.forename: Colin
authors.initials: C
authors.lastname: Nuckolls
mesh_terms: D015195:Drug Design; D047028:Macrocyclic Compounds / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D013237:Stereoisomerism; D013314:Stress, Mechanical
chemical_list: D047028:Macrocyclic Compounds