We report through-space (TS) (19)F-(19)F coupling for ortho-fluoro-substituted Z-azobenzenes. The magnitude of the TS-coupling constant ((TS) JFF ) ranged from 2.2-5.9 Hz. Using empirical formulas reported in the literature, these coupling constants correspond to non-bonded F-F distances (dFF) of 3.0-3.5 Å. These non-bonded distances are significantly smaller than those determined by X-ray crystallography or density functional theory, which argues that simple models of (19)F-(19)F TS spin-spin coupling solely based dFF are not applicable. (1)H, (13)C and (19)F data are reported for both the E and Z isomers of ten fluorinated azobenzenes. Density functional theory [B3YLP/6-311++G(d,p)] was used to calculate (19) F chemical shifts, and the calculated values deviated 0.3-10.0 ppm compared with experimental values.
Keywords: 13C; 19F; 1H; NMR; azobenzene; cis-azoenzene; fluorinated azobenzene; through-space coupling.
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