The introduction of chirality in organic conjugated polymers displaying electroconductive properties has been considered for a wide variety of purposes: 1) the ordered spontaneous chain assembling induced by chirality; 2) the noncentrosymmety associated to chiral materials, which is a prerequisite for second-order nonlinear optical applications; 3) the ability of chiral enantiomerically enriched molecules to discriminate between antipodes, as required in sensors designed for the detection of chiral analytes; 4) chiral electroconductive polymers could be used to modify the surface of electrodes to be employed in asymmetric redox reactions. Chirality is generally introduced in the polymer by attaching chiral pendants to the electroactive conjugated backbone through suitable linkers, and a great variety of chiral substituents have been employed either chosen from the chiral pool, like sugar and amino-acids, or man-made, designed and synthesized for specific applications. We have developed a new strategy for preparing electroactive chiral polymers, consisting in the oxidative polymerization of chiral oligothiophene monomers in which chirality results from a tailored torsion produced along the oligothiophene backbone by an atropisomeric bithiophene1 or bipyrrole scaffold (Scheme 1). The structural design of the monomers requires that the biheteroaromatic core would take part in the conjugative communication between the bithiophene termini. Furthermore, the polymerization sites of the monomers should be homotopic, thus granting the perfect constitutional regularity of the polymers. are reported The first examples of monomers designed according to this strategy (Scheme 1) and their electropolymerization to yield materials exhibiting outstanding chirality manifestations are discussed. References: 1) F. Sannicolò, S. Rizzo, T. Benincori, W. Kutner, K. Noworyta, J. W. Sobczak, V. Bonometti, L. Falciola, P. R. Mussini, M. Pierini, Electrochimica Acta, 2010,55, 8352; A. Pietrzyk, W. Kutner, R. Chitta, M. E. Zandler, F. D’Souza, F. Sannicolò, P. R. Mussini, Anal. Chem. 2009, 81, 10061.

C2-Symmetric Oligothiophene Monomers as Precursors of Inherently Chiral Semiconductors / F. Sannicolò, S. Rizzo, T. Benincori, P.R. Mussini, V. Bonometti, S. Abbate, R. Cirilli, M. Pierini. ((Intervento presentato al 13. convegno ROYAL SOCIETY OF CHEMISTRY-ITALIAN CHEMICAL SOCIETY JOINT MEETING ON HETEROCYCLIC CHEMISTRY tenutosi a CATANIA nel 2012.

C2-Symmetric Oligothiophene Monomers as Precursors of Inherently Chiral Semiconductors

F. Sannicolò
Primo
;
P.R. Mussini;V. Bonometti;
2012

Abstract

The introduction of chirality in organic conjugated polymers displaying electroconductive properties has been considered for a wide variety of purposes: 1) the ordered spontaneous chain assembling induced by chirality; 2) the noncentrosymmety associated to chiral materials, which is a prerequisite for second-order nonlinear optical applications; 3) the ability of chiral enantiomerically enriched molecules to discriminate between antipodes, as required in sensors designed for the detection of chiral analytes; 4) chiral electroconductive polymers could be used to modify the surface of electrodes to be employed in asymmetric redox reactions. Chirality is generally introduced in the polymer by attaching chiral pendants to the electroactive conjugated backbone through suitable linkers, and a great variety of chiral substituents have been employed either chosen from the chiral pool, like sugar and amino-acids, or man-made, designed and synthesized for specific applications. We have developed a new strategy for preparing electroactive chiral polymers, consisting in the oxidative polymerization of chiral oligothiophene monomers in which chirality results from a tailored torsion produced along the oligothiophene backbone by an atropisomeric bithiophene1 or bipyrrole scaffold (Scheme 1). The structural design of the monomers requires that the biheteroaromatic core would take part in the conjugative communication between the bithiophene termini. Furthermore, the polymerization sites of the monomers should be homotopic, thus granting the perfect constitutional regularity of the polymers. are reported The first examples of monomers designed according to this strategy (Scheme 1) and their electropolymerization to yield materials exhibiting outstanding chirality manifestations are discussed. References: 1) F. Sannicolò, S. Rizzo, T. Benincori, W. Kutner, K. Noworyta, J. W. Sobczak, V. Bonometti, L. Falciola, P. R. Mussini, M. Pierini, Electrochimica Acta, 2010,55, 8352; A. Pietrzyk, W. Kutner, R. Chitta, M. E. Zandler, F. D’Souza, F. Sannicolò, P. R. Mussini, Anal. Chem. 2009, 81, 10061.
Settore CHIM/06 - Chimica Organica
Settore CHIM/02 - Chimica Fisica
Settore CHIM/01 - Chimica Analitica
ROYAL SOCIETY OF CHEMISTRY
Società Chimica Italiana
http://www.dipchi.unict.it/joint2012/
C2-Symmetric Oligothiophene Monomers as Precursors of Inherently Chiral Semiconductors / F. Sannicolò, S. Rizzo, T. Benincori, P.R. Mussini, V. Bonometti, S. Abbate, R. Cirilli, M. Pierini. ((Intervento presentato al 13. convegno ROYAL SOCIETY OF CHEMISTRY-ITALIAN CHEMICAL SOCIETY JOINT MEETING ON HETEROCYCLIC CHEMISTRY tenutosi a CATANIA nel 2012.
Conference Object
File in questo prodotto:
Non ci sono file associati a questo prodotto.
Pubblicazioni consigliate

Caricamento pubblicazioni consigliate

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2434/191896
Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus ND
  • ???jsp.display-item.citation.isi??? ND
social impact