title: Potential-driven chirality manifestations and impressive enantioselectivity by inherently chiral electroactive organic films.
abstract: 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.
authors: Università di Milano, Dip. di Chimica and C.I.Ma.I.NA via Golgi 19, 20133 Milano (Italy). francesco.sannicolo@unimi.it.
authors: Francesco
authors: F
authors: Sannicolò
authors: Serena
authors: S
authors: Arnaboldi
authors: Tiziana
authors: T
authors: Benincori
authors: Valentina
authors: V
authors: Bonometti
authors: Roberto
authors: R
authors: Cirilli
authors: Lothar
authors: L
authors: Dunsch
authors: Włodzimierz
authors: W
authors: Kutner
authors: Giovanna
authors: G
authors: Longhi
authors: Patrizia R
authors: PR
authors: Mussini
authors: Monica
authors: M
authors: Panigati
authors: Marco
authors: M
authors: Pierini
authors: Simona
authors: S
authors: Rizzo
mesh_terms: D004583:Electrons; D006571:Heterocyclic Compounds / Q000737:chemistry*; D015394:Molecular Structure; D011108:Polymers / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D006571:Heterocyclic Compounds; D011108:Polymers
keywords: chirality; circular dichroism; electrochemistry; heterocycles; oligomerization