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Expanding the carbo ‐Benzene Chemical Space for Electron‐Accepting Ability: Trifluorotolyl/Tertiobutyl Substitution Balance
Author(s) -
Chammam Marwa,
CaballeroQuintana Irving,
BarreiroArgüelles Denisse,
AmargósReyes Olivia,
Aidibi Youssef,
Kauffmann Brice,
Duhayon Carine,
Maldonado JoséLuis,
RamosOrtíz Gabriel,
Maraval Valérie,
Chauvin Remi
Publication year - 2019
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.201900049
Subject(s) - chemistry , benzene , crystallography , solubility , medicinal chemistry , stereochemistry , organic chemistry
With the view to altering the lipophilicity and electron accepting ability of the tetraphenyl‐ carbo ‐benzene scaffold, peripheral fluorination of the C 18 ring through aromatic linkers was envisaged from the C 18 Ph 6 and o ‐ t Bu 2 C 18 Ph 4 references, by replacement of two Ph substituents with two p ‐CF 3 ‐C 6 H 4 counterparts ( F Tol). 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 ‐ F Tol 2 C 18 Ph 4 proved to be hardly tractable due to an extremely low solubility, p ‐ F Tol 2 ‐ o ‐ t Bu 2 C 18 Ph 2 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 PC 71 BM 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 CF 3 groups, in agreement with the DFT‐calculated frontier orbitals and multipole moments. The results provide guidelines for optimization of fluorinated carbo ‐benzene targets.