通过自组装分子笼的光化学激发实现烷烃氧化。

Alkane oxidation via photochemical excitation of a self-assembled molecular cage.

作者信息

Yoshizawa Michito, Miyagi Sachiko, Kawano Masaki, Ishiguro Katsuya, Fujita Makoto

机构信息

Department of Applied Chemistry, School of Engineering, The University of Tokyo, and CREST, Japan Science and Technology Corporation (JST), Bunkyo-ku, Tokyo 113-8656, Japan.

出版信息

J Am Chem Soc. 2004 Aug 4;126(30):9172-3. doi: 10.1021/ja047612u.

DOI:10.1021/ja047612u

PMID:15281793

Abstract

The photoexcitation of a self-assembled M6L4-type coordination cage accommodating photochemically inert alkane guests (e.g., adamantane and cyclooctane) led to the regioselective oxidation of the guest within the cage. Under anaerobic conditions, the guest oxidation was accompanied by the stable radical formation as indicated by ESR spectrometry (g = 2.002) and change in solution color (from colorless to blue). These phenomena were shown to be characteristic of the self-assembled molecular systems: i.e., from the M6L4 supersetGn assembly, none of the components (M, L, or G) can be eliminated for the unusual oxidation and/or radical formation.

摘要

容纳光化学惰性烷烃客体（如金刚烷和环辛烷）的自组装M6L4型配位笼的光激发导致笼内客体的区域选择性氧化。在厌氧条件下，客体氧化伴随着稳定自由基的形成，这通过电子自旋共振光谱法（g = 2.002）和溶液颜色变化（从无色变为蓝色）得以表明。这些现象被证明是自组装分子体系的特征：即，对于不寻常的氧化和/或自由基形成，M6L4超集Gn组装体中的任何组分（M、L或G）都不能被去除。