Structure and spectroscopic characterization of tetrathia- and tetraselena[8]circulenes as a new class of polyaromatic heterocycles

• Vibrational spectra of tetrathia[8]circulene and tetraselena[8]circulene were measured.
• Vibrational spectra were also calculated and interpreted by the DFT method.
• The comparing with the parent tetraoxa[8]circulene was made.
• Both circulenes possess the bifacial aromatic/antiaromatic nature.
• The first S0 → S1 electronic transition for both molecules is symmetry allowed.

The FTIR, Raman and UV–vis spectra of the recently synthesized tetrathia[8]circulene and tetraselena[8]circulene compounds have been measured and interpreted in details by the density functional theory (DFT) calculations taking into account the molecular symmetry constrains. The structural and electronic features of the studied compounds have also been discussed in connection with the observed spectroscopic characteristics. Particularly, we have found that despite a slightly non-planar conformation the neutral tetrathia[8]circulene and tetraselena[8]circulene molecules demonstrate bifacial aromatic/antiaromatic nature. The inner octatetraene core is characterized by the presence of paratropic (“antiaromatic”) ring currents, whereas the outer macrocycle constructed of benzene, thiophene or selenophene rings possesses the strong magnetically-induced diatropic (“aromatic”) ring current. This fact suggests the general electronic and magnetic similarity of the tetrathia- and tetraselena[8]circulenes with the strictly planar isoelectronic tetraoxa[8]circulene and related azaoxa-derivatives discussed earlier. However, the vibrational and UV–vis absorption spectra of the studied circulenes are rather different from those of the parent tetraoxa[8]circulene which indicates a clear manifestation of the symmetry selection rules.

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