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EthylenedithioTetrathiafulvaleneHelicenes: Electroactive Helical Precursors with Switchable Chiroptical Properties
Author(s) -
Biet Thomas,
Fihey Arnaud,
Cauchy Thomas,
Vanthuyne Nicolas,
Roussel Christian,
Crassous Jeanne,
Avarvari Narcis
Publication year - 2013
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201301095
Subject(s) - helicene , tetrathiafulvalene , enantiopure drug , chemistry , circular dichroism , dihedral angle , crystallography , redox , stereochemistry , photochemistry , molecule , enantioselective synthesis , organic chemistry , hydrogen bond , catalysis
Electroactive fused ethylenedithiotetrathiafulvalene[4]helicene and ‐[6]helicenes have been synthesized through a strategy that involved the preparation of 2,3‐dibromo‐helicene derivatives as intermediates. The dihedral angles between the terminal helicenes, as determined by single‐crystal X‐ray analysis, are 22.7° and 50.7° for the [4]helicene and [6]helicene, respectively. Their solid‐state architectures show interplay between S⋅⋅⋅S and π⋅⋅⋅π intermolecular interactions. The chiroptical properties of the enantiopure EDTTTF[6]helicene derivatives have been investigated and supported by TDDFT calculations. Remarkable redox switching of the circular dichroism (CD) signal between the neutral and radical‐cation species has been achieved.