Chiral Conjugated Corrals

被引：101

作者：

Ball, Melissa ^{[2
]}

Fowler, Brandon ^{[2
]}

Li, Panpan ^{[1
,2
]}

Joyce, Leo A. ^{[3
]}

Li, Fang ^{[1
]}

Liu, Taifeng ^{[1
]}

Paley, Daniel ^{[2
]}

Zhong, Yu ^{[2
]}

Li, Hexing ^{[1
]}

Xiao, Shengxiong ^{[1
]}

Ng, Fay ^{[2
]}

Steigerwald, Michael L. ^{[2
]}

Nuckolls, Colin ^{[1
,2
]}

机构：

[1] Shanghai Normal Univ, Shanghai Key Lab Rare Earth Funct Mat, Optoelect Nano Mat & Devices Inst, Educ Minist,Key Lab Resource Chem,Dept Chem, Shanghai 200234, Peoples R China

[2] Columbia Univ, Dept Chem, New York, NY 10027 USA

[3] Merck Res Labs, Proc & Analyt Chem, Rahway, NJ 07065 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2015年 / 137卷 / 31期

关键词：

BAND-GAP; MEDIATED SYNTHESIS; CARBON NANORINGS; PERYLENE; CYCLOPARAPHENYLENES; DEPENDENCE; POLYMERS; STEP;

D O I：

10.1021/jacs.5b05698

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

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 g-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 diirnide 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.

引用

页码：9982 / 9987

页数：6

共 51 条

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