Expanding the carbo‐Benzene Chemical Space for Electron‐Accepting Ability: Trifluorotolyl/Tertiobutyl Substitution Balance

With the view to altering the lipophilicity and electron accepting ability of the tetraphenyl‐carbo‐benzene scaffold, peripheral fluorination of the C₁₈ ring through aromatic linkers was envisaged from the C₁₈Ph₆ and o‐^tBu₂C₁₈Ph₄ references, by replacement of two Ph substituents with two p‐CF₃‐C₆H₄ counterparts (^FTol). The synthesis relied on a [8+10] macrocyclization involving a common bis(trifluorotolyl)‐tetraynedione, followed by reductive aromatization of the resulting [6]pericyclynediols. While p‐^FTol₂C₁₈Ph₄ proved to be hardly tractable due to an extremely low solubility, p‐^FTol₂‐o‐^tBu₂C₁₈Ph₂ could be extensively studied by X‐ray crystallography, NMR and UV/Vis spectroscopy, voltammetry, STM imaging of monolayers, and AFM imaging of binary films with P3HT or PC₇₁BM fabricated by spin‐coating for organic photovoltaic cells and J?V curve measurement thereof. The electronic and polarity properties are correlated with moderate but consistent electron‐withdrawing effects of the CF₃ groups, in agreement with the DFT‐calculated frontier orbitals and multipole moments. The results provide guidelines for optimization of fluorinated carbo‐benzene targets.