The Smallest Stable Fullerene, M@C28 (M = Ti, Zr, U): Stabilization and Growth from Carbon Vapor

详细信息    查看全文

• 作者：Paul W. Dunk ; Nathan K. Kaiser ; Marc Mulet-Gas ; Antonio Rodr铆guez-Fortea ; Josep M. Poblet ; Hisanori Shinohara ; Christopher L. Hendrickson ; Alan G. Marshall ; Harold W. Kroto
• 刊名：The Journal of the American Chemical Society
• 出版年：2012
• 出版时间：June 6, 2012
• 年：2012
• 卷：134
• 期：22
• 页码：9380-9389
• 全文大小：488K
• 年卷期：v.134,no.22(June 6, 2012)
• ISSN：1520-5126

文摘

The smallest fullerene to form in condensing carbon vapor has received considerable interest since the discovery of Buckminsterfullerene, C₆₀. Smaller fullerenes remain a largely unexplored class of all-carbon molecules that are predicted to exhibit fascinating properties due to the large degree of curvature and resulting highly pyramidalized carbon atoms in their structures. However, that curvature also renders the smallest fullerenes highly reactive, making them difficult to detect experimentally. Gas-phase attempts to investigate the smallest fullerene by stabilization through cage encapsulation of a metal have been hindered by the complexity of mass spectra that result from vaporization experiments which include non-fullerene clusters, empty cages, and metallofullerenes. We use high-resolution FT-ICR mass spectrometry to overcome that problem and investigate formation of the smallest fullerene by use of a pulsed laser vaporization cluster source. Here, we report that the C₂₈ fullerene stabilized by encapsulation with an appropriate metal forms directly from carbon vapor as the smallest fullerene under our conditions. Its stabilization is investigated, and we show that M@C₂₈ is formed by a bottom-up growth mechanism and is a precursor to larger metallofullerenes. In fact, it appears that the encapsulating metal species may catalyze or nucleate endohedral fullerene formation.