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Vibrational Raman optical activity of pi-conjugated helical systems: Hexahelicene and heterohelicenes.

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Liégeois, Vincent Champagne, Benoît

Helicenes constitute a special class of molecules combining helical conformation with pi-electron delocalization. These confer to helicenes specific chirooptical properties. In this article, we investigate the vibrational signatures thanks to the simulation of vibrational Raman optical activity (VROA) spectra. For that, four representative helicenes: hexahelicene, tetrathia-[7]-helicene, and its pyrrole and furan analogs have been simulated and interpreted using a recently implemented analytical scheme. Helicenes show intense VROA peaks attributed to their pi-conjugated structure and associated with collective vibrational modes. In hexahelicene, the dominant VROA features are due to vibrational modes involving motions of the carbon skeleton and H-wagging, but the intensity finds its source almost exclusively in the former. In the case of the three heterohelicenes, the previous statement is also verified, and on changing the heteroatoms, similar modes presenting comparable atomic contribution patterns have been highlighted, though the vibrational and electronic properties are modified. Some fingerprints could therefore be associated with the helicity of the system. In particular, in forward spectra, most of the VROA bands are positive for left-handed helicenes. Nevertheless, the spectral patterns are quite complex, and no easy rule-of-thumb could distinguish between the different heterohelicenes. Then, considering the fact that most of the contributions originate from the C atoms (group coupling matrices decomposition), it can be concluded that the major role of the heteroatom is restricted to modifying the geometry and the normal modes. At last, the small impact of the gauge-origin on the calculated spectra using a relatively modest basis set (rDPS:3-21G) is demonstrated here in the case of the tetrathia-[7]-helicene molecule presenting a C(2) symmetry. This further demonstrates the adequacy of this basis set for VROA calculations. (c) 2008 Wiley Periodicals, Inc. J Comput Chem, 2009.

Document type Article de périodique (Journal article) – Journal Article
Publication date 2008
Journal information "Journal of computational chemistry" - Vol. 30, no. 8, p. 1261-78 (2009)
Peer reviewed yes
e-issn 1096-987X
issn 0192-8651
Publication status Publié
Affiliation UCL
MESH Subject Vibration ; Spectrum Analysis, Raman ; Pyrroles - chemistry ; Polycyclic Compounds - chemistry ; Models, Chemical ; Furans - chemistry ; Computer Simulation
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Bibliographic reference Liégeois, Vincent ; Champagne, Benoît. Vibrational Raman optical activity of pi-conjugated helical systems: Hexahelicene and heterohelicenes.. In: Journal of computational chemistry, Vol. 30, no. 8, p. 1261-78 (2009)
Permanent URL http://hdl.handle.net/2078.2/19696