As mentioned in the Introduction, Bonomo et al. reported the presence of three isomers in similar trithiophenes based on 1 H NMR measurements, which closely resemble our NMR data. However, they concluded that these isomers were conformers arising from the rotation of the terminal thiophene rings in the ZZ isomer rather than geometric isomers. The geometric nature of these isomers was established based on our 2D NMR analyses and X-ray crystallographic studies (vide infra). Moreover, computational studies by Bonomo et al. have predicted a relatively low activation barrier of 6-7 kcal/mol for the terminal thiophene ring rotation. If this were correct, the interconversion rate would be faster than the NMR timescale, likely resulting in coalescence of the isomer signals at room temperature. Our observation of slow interconversion among the isomers also strongly supports the idea that three isomers arise from the E/Z configurations.