Demonstration of a chemical transformation inside a fullerene. The reversible conversion of the allotropes of H2@C60

Nicholas J. Turro, Angel A. Martí, Judy Y.C. Chen, Steffen Jockusch, Ronald G. Lawler, Marco Ruzzi, Elena Sartori, Shih-Ching Chuang, Koichi Komatsu, Yasujiro Murata

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Abstract

The interconversion of the two allotropes of the hydrogen molecule (para-H2 and ortho-H2) incarcerated inside the fullerene C60 is reported (oH2@C60 and pH2@C60, respectively). For conversion, oH2@C60 was adsorbed at the external surface of the zeolite NaY and immersed into liquid oxygen at 77 K. Equilibrium was reached in less than 0.5 h. Rapid removal of oxygen provides a sample of enriched pH2@C60 that is stablefor many days in the absence of paramagnetic catalysts (half-life ∼15 days). Enriched pH2@C60 is nonvolatile and soluble in organic solvents. At room temperature in the presence of a paramagnetic catalyst (dissolved O2 or the nitroxide Tempo) a slow back conversion into oH2@C60 was observed by 1H NMR. A bimolecular rate constant for conversion of pH2@C60 to oH2@C60 using Tempo of kTempo ∼4 × 10-5 M-1 s-1 was observed, which is approximately 3 orders of magnitudes slower than that for dissolved pH2 in organic solvents which is not protected by the C60 shell.

Original languageEnglish
Pages (from-to)10506-10507
Number of pages2
JournalJournal of the American Chemical Society
Volume130
Issue number32
DOIs
StatePublished - 13 Aug 2008

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    Turro, N. J., Martí, A. A., Chen, J. Y. C., Jockusch, S., Lawler, R. G., Ruzzi, M., Sartori, E., Chuang, S-C., Komatsu, K., & Murata, Y. (2008). Demonstration of a chemical transformation inside a fullerene. The reversible conversion of the allotropes of H2@C60. Journal of the American Chemical Society, 130(32), 10506-10507. https://doi.org/10.1021/ja804311c