Lipidic Carbo-benzenes: Molecular Probes of Magnetic Anisotropy and Stacking Properties of α-Graphyne.

Solubilization of the C fundamental circuit of α-graphyne has been envisaged by decoration with aliphatic chains R = n-CH. The synthesis and characterization of p-dialkyl-tetraphenyl-carbo-benzenes (n = 2, 8, 14, 20) are thus presented and compared to the monoalkyl series produced concomitantly. In both series, a dramatic enhancement of solubility in organic solvents (CHCl, CHCl) is observed for n ≥ 8, and in the dialkyl series, the melting-decomposition temperature of the solid products is shown to decrease linearly from 208 °C for n = 2 to 149 °C for n = 20. Fluoroalkyl analogues with R = n-CHF are also described. The products display classical UV-vis electronic spectra of carbo-benzenes in solution (λ = 445.5 ± 1 nm, ε ≈ 200 000 L·mol·cm). They are also characterized by UV-vis absorption in the solid state, which is found to be correlated with the color and crystal packing. The methylene groups of R provide an experimental probe of the magnetic anisotropy and aromaticity of the C ring through the progressive NMR shielding of the H nuclei from ca. 4.70 to 1.25 ppm going away from the border of the ring (as far as 8 Å away). All alkyl-carbo-benzenes were also found to be highly crystalline. Seven of them have been characterized by X-ray diffraction analysis and the C columnar packing compared in a systematic manner. Crystals of the diethyl and bistetradecyl derivatives, containing no solvent molecule, provided the first examples of direct π-stacking of carbo-benzene rings, with inter-ring distances very close to calculated interlayer distances in AB and ABC α-graphityne (3.255 and 3.206 Å vs 3.266 and 3.201 Å, respectively).