Reversible Dimerization and Polymerization of a Janus Diradical To Produce Labile C−C Bonds and Large Chromic Effects

José L. Zafra, Lili Qiu, Naoyuki Yanai, Takamichi Mori, Masahiro Nakano, Miriam Peña Alvarez, Juan T.López Navarrete, Carlos J. Gómez-García, Miklos Kertesz, Kazuo Takimiya, Juan Casado

Research output: Contribution to journalArticle

27 Citations (Scopus)

Abstract

Conducting polymers can be synthesized by irreversible diradical monomer polymerization. A reversible version of this reaction consisting of the formation/dissociation of σ-dimers and σ-polymers from a stable quinonoidal diradical precursor is described. The reaction reversibility is made by a quinonoidal molecule which changes its structure to an aromatic species by forming weak and long intermolecular C−C single bonds. The reaction provokes a giant chromic effect of about 2.5 eV. The two opposite but complementary quinonoidal and aromatic tautomers provide the Janus faces of the reactants and products which produces the observed chromic effect. A reaction mechanism is proposed to explain the variety of final products starting with structurally very similar reactants. These reversible reactions, covering an unusual regime of weak covalent supramolecular bonding, yield products which might be envisaged as novel molecular and polymeric soft matter phases.

Original languageEnglish
Pages (from-to)14563-14568
Number of pages6
JournalAngewandte Chemie - International Edition
Volume55
Issue number47
DOIs
Publication statusPublished - 2016 Jan 1
Externally publishedYes

Keywords

  • cyclophanes
  • density functional calculations
  • radicals
  • reaction mechanisms
  • solvatochromism

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

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    Zafra, J. L., Qiu, L., Yanai, N., Mori, T., Nakano, M., Alvarez, M. P., Navarrete, J. T. L., Gómez-García, C. J., Kertesz, M., Takimiya, K., & Casado, J. (2016). Reversible Dimerization and Polymerization of a Janus Diradical To Produce Labile C−C Bonds and Large Chromic Effects. Angewandte Chemie - International Edition, 55(47), 14563-14568. https://doi.org/10.1002/anie.201605997