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

Xue-Bin Wang; Chaoxian Chi; Mingfei Zhou; Igor V Kuvychko; Konrad Seppelt; Alexey A Popov; Steven H Strauss; Olga V Boltalina; Lai-Sheng Wang

doi:10.1021/jp9097364

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

J Phys Chem A. 2010 Feb 4;114(4):1756-65. doi: 10.1021/jp9097364.

Authors

Xue-Bin Wang¹, Chaoxian Chi, Mingfei Zhou, Igor V Kuvychko, Konrad Seppelt, Alexey A Popov, Steven H Strauss, Olga V Boltalina, Lai-Sheng Wang

Affiliation

¹ Department of Physics, Washington State University, Richland, Washington 99354, USA.

PMID: 20058887
DOI: 10.1021/jp9097364

Abstract

A photoelectron spectroscopy investigation of the fluorofullerene anions C(60)F(n)(-) (n = 17, 33, 35, 43, 45, 47) and the doubly charged anions C(60)F(34)(2-) and C(60)F(46)(2-) is reported. The first electron affinities for the corresponding neutral molecules, C(60)F(n), were directly measured and were found to increase as n increased, reaching the extremely high value of 5.66 +/- 0.10 eV for C(60)F(47). Density functional calculations suggest that the experimentally observed species C(60)F(17)(-), C(60)F(35)(-), and C(60)F(47)(-) were each formed by reductive defluorination of the parent fluorofullerene, C(3v)-C(60)F(18), C(60)F(36) (a mixture of isomers), and D(3)-C(60)F(48), respectively, without rearrangement of the remaining fluorine atoms. The DFT-predicted stability of C(60)F(47)(-) was verified by its generation by chemical reduction from D(3)-C(60)F(48) in chloroform solution at 25 degrees C and its characterization by mass spectrometry and (19)F NMR spectroscopy. Further reductive defluorination of C(60)F(47)(-) in solution resulted in the selective generation of a new fluorofullerene, D(2)-C(60)F(44), which was also characterized by mass spectrometry and (19)F NMR spectroscopy.