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
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.
- Research Organization:
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- AC05-76RL01830
- OSTI ID:
- 974943
- Report Number(s):
- PNNL-SA-68844; 25395; KC0301020; KP1704020; TRN: US201013%%426
- Journal Information:
- Journal of Physical Chemistry A, 114(4):1756-1765, Vol. 114, Issue 4
- Country of Publication:
- United States
- Language:
- English
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