期刊
CHEMICAL SCIENCE
卷 3, 期 5, 页码 1399-1407出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c2sc01133f
关键词
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资金
- U.S. NSF [CHE-0707223, CHE-1012468, CHE-0822838]
- Colorado State University Research Foundation
- U.S. Department of Energy (DOE), Division of Chemical Sciences, Geosciences and Biosciences, Office of Basic Energy Sciences
- DOE's Office of Biological and Environmental Research at Pacific Northwest National Laboratory
- PNNL
- U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences [DE-AC02-06CH11357]
- The AvH Foundation
- The Erasmus Mundus Program External Co-operation [EM ECW-L04 TUD 08-11]
- The Electrochemical Society
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [0822838] Funding Source: National Science Foundation
A series of seven structurally-similar compounds with different pairs of R-F groups were prepared, characterized spectroscopically, and studied by electrochemical methods (cyclic and square-wave voltammetry), low-temperature anion photoelectron spectroscopy, and DFT calculations (five of the compounds are reported here for the first time). This is the first time that a set of seven R-F groups have been compared with respect to their relative effects on E-1/2(0/-), electron affinity (EA), and the DFT-calculated LUMO energy. The compounds, 1,7-C-60(R-F)(2) (R-F = CF3, C2F5, i-C3F7, n-C3F7, s-C4F9, n-C4F9 and n-C8F21), were found to have statistically different electron affinities (EA), at the +/- 10 meV level of uncertainty, but virtually identical first reduction potentials, at the +/- 10 mV level of uncertainty. The lack of a correlation between EA and E-1/2(0/-), and between E(LUMO) and E-1/2(0/-), for such similar compounds is unprecedented and suggests that explanations for differences in figures of merit for materials and/or devices that are based on equating easily measurable E-1/2(0/-) values with EAs or E(LUMO) values should be viewed with caution. The solubilities of the seven compounds in toluene varied by nearly a factor of six, but in an unpredictable way, with the C2F5 and s-C4F9 compounds being the most soluble and the i-C3F7 compound being the least soluble. The effects of the different R-F groups on EAs, E(LUMO) values, and solubilities should help fluorine chemists choose the right R-F group to design new materials with improved morphological, electronic, optical, and/or magnetic properties.
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