Photoelectron Spectroscopy of C60Fn - and C60Fm 2- (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

摘要

A photoelectron spectroscopy investigation of the fluorofullerene anions C60Fn - (n ) 17, 33, 35, 43, 45, 47) and the doubly charged anions C60F34 2- and C60F46 2- is reported. The first 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