4.8 Article

Infinitene: A Helically Twisted Figure-Eight [12]Circulene Topoisomer

期刊

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 144, 期 2, 页码 862-871

出版社

AMER CHEMICAL SOC
DOI: 10.1021/jacs.1c10807

关键词

-

资金

  1. ERATO program from JST [JPMJER1302]
  2. JST-CREST program [JPMJCR19R1]
  3. JSPS KAKENHI [19H05463, JP20K21192, JP21H01931, JP18H02019]
  4. Noguchi Research Foundation
  5. Yazaki Memorial Foundation for Science and Technology
  6. JSPS
  7. World Premier International Research Center Initiative (WPI), Japan

向作者/读者索取更多资源

A new infinity-shaped polyarene, infinitene (1), with unique molecular structure and stability, exhibits distinctive photophysical properties, making it a topoisomer of certain carbon nanostructures.
New forms of molecular nanocarbon particularly looped polyarenes adopting various topologies contribute to the fundamental science and practical applications. Here we report the synthesis of an infinity-shaped polyarene, infinitene (1) (cyclo[c.c.c.c.c.c.e.e.e.e.e.e]-dodecakisbenzene), comprising consecutively fused 12-benzene rings forming an enclosed loop with a strain energy of 60.2 kcal.mol(-1). Infinitene (1) represents a topoisomer of still-hypothetical [12]circulene, and its scaffold can be formally visualized as the outcome of the stitching of two homochiral [6]helicene subunits by both their ends. The synthetic strategy encompasses transformation of a rationally designed dithiacyclophane to cyclophadiene through the Stevens rearrangement and pyrolysis of the corresponding S,S'-bis(oxide) followed by the photocyclization. The structure of 1 is a unique hybrid of helicene and circulene with a molecular formula of C48H24, which can be regarded as an isomer for kekulene, [6,6]carbon nanobelt ([6,6]CNB), and [12]cyclacene. Infinitene (1) is a bench-stable yellow solid with green fluorescence and soluble to common organic solvents. Its figure-eight molecular structure was unambiguously confirmed by X-ray crystallography. The scaffold of 1 is significantly compressed as manifested by a remarkably shortened distance (3.152-3.192 angstrom) between the centroids of two pi-pi stacked central benzene rings and the closest C center dot center dot center dot C distance of 2.920 angstrom. Fundamental photophysical properties of 1 were thoroughly elucidated by UV-vis absorption and fluorescence spectroscopic studies and density functional theory calculations. Its configurational stability enabled separation of the corresponding enantiomers (P,P) and (M,M) by a chiral HPLC. Circular dichroism (CD) and circularly polarized luminescence (CPL) measurements revealed that 1 has moderate vertical bar gCD vertical bar and vertical bar gCPL vertical bar values.

作者

我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。

评论

主要评分

4.8
评分不足

次要评分

新颖性
-
重要性
-
科学严谨性
-
评价这篇论文

推荐

暂无数据
暂无数据