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

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

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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.


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.


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