We gratefully acknowledge the support of Prof. Sergio Abbate and Dr. Ettore Castiglioni (polymers CD measurements), Dr. Letizia Colella (Organic synthesis), Dr. Mirko Magni and Dr. Ester Giussani (EIS and enantiorecognition tests), Dr. Krzysztof Noworyta (EQCM), Dr. Sergio Menta (Chiral HPLC), Dr. Kinga Haubner (EPR spectroelectro chemistry), and Prof. A. Gennaro and Dr. A. A. Isse (scientific discussions). With the contribution of Fondazione Cariplo, grant no. 2011-0417.
Potential-Driven Chirality Manifestations and Impressive Enantioselectivity by Inherently Chiral Electroactive Organic Films†
Article first published online: 5 FEB 2014
© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Angewandte Chemie International Edition
Volume 53, Issue 10, pages 2623–2627, March 3, 2014
How to Cite
Sannicolò, F., Arnaboldi, S., Benincori, T., Bonometti, V., Cirilli, R., Dunsch, L., Kutner, W., Longhi, G., Mussini, P. R., Panigati, M., Pierini, M. and Rizzo, S. (2014), Potential-Driven Chirality Manifestations and Impressive Enantioselectivity by Inherently Chiral Electroactive Organic Films. Angew. Chem. Int. Ed., 53: 2623–2627. doi: 10.1002/anie.201309585
- Issue published online: 25 FEB 2014
- Article first published online: 5 FEB 2014
- Manuscript Received: 4 NOV 2013
- circular dichroism;
The typical design of chiral electroactive materials involves attaching chiral pendants to an electroactive polyconjugated backbone and generally results in modest chirality manifestations. Discussed herein are electroactive chiral poly-heterocycles, where chirality is not external to the electroactive backbone but inherent to it, and results from a torsion generated by the periodic presence of atropisomeric, conjugatively active biheteroaromatic scaffolds, (3,3′-bithianaphthene). As the stereogenic element coincides with the electroactive one, films of impressive chiroptical activity and outstanding enantiodiscrimination properties are obtained. Moreover, chirality manifestations can be finely and reversibly tuned by the electric potential, as progressive injection of holes forces the two thianaphthene rings to co-planarize to favor delocalization. Such deformations, revealed by CD spectroelectrochemistry, are elastic and reversible, thus suggesting a breathing system.