Department of Chemistry and Chemical Biology, Cornell University, Baker Laboratory, Ithaca, NY 14853-1301, USA.
Phys Chem Chem Phys. 2012 Aug 21;14(31):10935-43. doi: 10.1039/c2cp41325f. Epub 2012 Jul 4.
The first comprehensive theoretical investigation of a series of functionalized fullerene cations, {R-C(60)}(+), where R = H, CH(3), CH(2)Cl, CHCl(2), and CCl(3), is accomplished. A detailed consideration of conformational energetic profiles of these systems resulted in the structures of most stable conformers that fit all available experimental data. The trends in stability of {R-C(60)}(+) cations as well as transition barriers for migration of alkyl groups over the C(60)-surface are provided. A thorough study of energetics of {R-C(60)}(+) is augmented by in-depth investigation of their electronic structures and aromaticity. As the final part of this study, the detailed comparison of structures, energetics and properties of {R-C(60)}(+) with those of corannulene cations, {R-hub-C(20)H(10)}(+), is performed at the same level of theory. The similarities and differences between the surface functionalized ball- and bowl-shaped carbocations are illuminated.
对一系列功能化富勒烯阳离子，{R-C(60)}（+），其中 R = H、CH(3)、CH(2)Cl、CHCl(2) 和 CCl(3)，进行了全面的理论研究。对这些系统的构象能谱的详细考虑导致了最稳定构象的结构，这些构象符合所有可用的实验数据。提供了 {R-C(60)}（+）阳离子稳定性的趋势以及烷基在 C(60)-表面上迁移的过渡势垒。通过深入研究它们的电子结构和芳香性，对 {R-C(60)}（+）的能态进行了彻底的研究。作为这项研究的最后一部分，在相同的理论水平上，对 {R-C(60)}（+）与corannulene 阳离子，{R-hub-C(20)H(10)}（+）的结构、能态和性质进行了详细的比较。阐明了表面官能化的球型和碗型碳阳离子之间的异同。
