Internal dynamics in helical molecules studied by X-ray diffraction, NMR spectroscopy and DFT calculations

Literature Information

Publication Date 2017-01-03
DOI 10.1039/C6CP07552E
Impact Factor 3.676
Authors

Martin Dračínský, Jan Storch, Vladimír Církva, Ivana Císařová, Jan Sýkora


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Abstract

The conformational behaviour of a prototype helical molecule, [6]helicene, and its derivatives was studied in solution and the solid state. Available crystal structures of [6]helicene revealed surprisingly large flexibility of this molecule and variable-temperature NMR experiments provided unusual temperature dependence of chemical shifts of hydrogen, carbon and fluorine atoms in the peripheral aromatic rings of [6]helicene and tetrafluoro[6]helicene. These chemical shift changes were interpreted as a consequence of the helicene ‘pitch’ opening with elevated temperature, and the experimental data were corroborated by DFT calculations of the chemical shift dependence on the helicene conformation and by variable-temperature DFT molecular dynamics simulations.

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