Probing Peripheral H-Bonding Functionalities in BN-Doped Polycyclic Aromatic Hydrocarbons

J. Tasseroul, M. M. Lorenzo-Garcia, J. Dosso, F. Simon, S. Velari, A. De Vita, P. Tecilla, D. Bonifazi

J. Org. Chem., 2020, 85, 5, 3454–3464.

DOI: 10.1021/acs.joc.9b03202


The replacement of carbon atoms at the zigzag periphery of a benzo[fg]tetracenyl derivative with an NBN atomic triad allows the formation of heteroatom-doped polycyclic aromatic hydrocarbon (PAH) isosteres, which expose BN mimics of the amidic NH functions. Their ability to form H-bonded complexes has never been touched so far. Herein, we report the first solution recognition studies of peripherally NBN-doped PAHs to form H-bonded DD·AA- and ADDA·DAAD-type complexes with suitable complementary H-bonding acceptor partners. The first determination of Ka in solution showed that the 1:1 association strength is around 27 ± 1 M–1 for the DD·AA complexes in C6D6, whereas it rises to 1820 ± 130 M–1 for the ADDA·DAAD array in CDCl3. Given the interest of BN-doped polyaromatic hydrocarbons in supramolecular and materials chemistry, it is expected that these findings will open new possibilities to design novel materials, where the H-bonding properties of peripheral NH hydrogens could serve as anchors to tailor the organizational properties of PAHs.

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