Photoelectron Spectroscopy of C60Fn- and C60Fm2- (n=17,33,35,43,45,47;m=34,46) in the Gas Phase and the Generation and Characterization of C1-C60F47- and D2-C60F44 in Solution

February 4, 2010

Journal Article

Photoelectron Spectroscopy of C60Fn- and C60Fm2- (n=17,33,35,43,45,47;m=34,46) in the Gas Phase and the Generation and Characterization of C1-C60F47- and D2-C60F44 in Solution

Abstract

A photoelectron spectroscopy investigation of the fluorofullerene anions C60Fn- (n = 17, 33, 35, 43, 45, 47) and the doubly-charged anions C60F342- and C60F462- is reported. The electron affinities for the corresponding neutral molecules, C60Fn, were directly measured and were found to increase as n increased, reaching the extremely high value of 5.66 ± 0.10 eV for C60F47. Density functional calculations suggest that the experimentally observed species C60F17-, C60F35-, and C60F47- were each formed by reductive-defluorination of the parent fluorofullerene, C3v-C60F18, C60F36 (a mixture of isomers), and D3-C60F48, respectively, without rearrangement of the remaining fluorine atoms. The DFT-predicted stability of C60F47- was verified by its generation by chemical reduction from D3-C60F48 in chloroform solution at 25 °C and its characterization by mass spectrometry and 19F NMR spectroscopy. Further reductive-defluorination of C60F47- in solution resulted in the selective generation of a new fluorofullerene, D2-C60F44, which was also characterized by mass spectrometry and 19F NMR spectroscopy.

Revised: October 5, 2010 | Published: February 4, 2010

Citation

Wang X.B., C. Chi, M. Zhou, I.V. Kuvychko, K. Seppelt, A.A. Popov, and S.H. Strauss, et al. 2010. Photoelectron Spectroscopy of C60Fn- and C60Fm2- (n=17,33,35,43,45,47;m=34,46) in the Gas Phase and the Generation and Characterization of C1-C60F47- and D2-C60F44 in Solution. Journal of Physical Chemistry A 114, no. 4:1756-1765. PNNL-SA-68844.