Chiral Conjugated Corrals.
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 th...
| Published in: | Journal of the American Chemical Society Vol. 137; no. 31; pp. 9982 - 9988 |
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| Main Authors: | , , , , , , , , , , , , |
| Format: | Article |
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American Chemical Society
8/12/2015
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| Subjects: | |
| Online Access: | View this record in EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=109275280&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 109275280 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 8/12/2015 vid: 137 iid: 31 pid: 997 pub: American Chemical Society artinfo: ui: 109275280 10.1021/jacs.5b05698 ppf: 9982 ppct: 6 formats: tig: atl: Chiral Conjugated Corrals. aug: au: Ball, Melissa Fowler, Brandon Panpan Li Joyce, Leo A. Fang Li Taifeng Liu Paley, Daniel Yu Zhong Hexing Li Shengxiong Xiao Fay Ng Steigerwald, Michael L. Nuckolls, Colin affil: Department of Chemistry, Columbia University, New York, New York 10027, United States The Education Ministry Key Lab of Resource Chemistry, Shanghai Key Laboratoiy of Rare Earth Functional Materials, Optoelectronic Nano Materials and Devices Institute, Department of Chemistry, Shanghai Normal University, Shanghai, China 200234 Process and Analytical Chemistry, Merck Research Laboratories, Rahway, New Jersey 07065, United States su: Macrocyclic compounds Corrals Electron donors Electrophiles Perylene Thiophenes Chirality Density functional theory sug: subj: Macrocyclic compounds Corrals Electron donors Electrophiles Perylene Thiophenes Chirality Density functional theory ab: 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 Tt-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. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2015 holdings: @attributes: islocal: N |
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