TY - JOUR
T1 - Reversible Dimerization and Polymerization of a Janus Diradical To Produce Labile C−C Bonds and Large Chromic Effects
AU - Zafra, Jose L.
AU - Qiu, Lili
AU - Yanai, Naoyuki
AU - Mori, Takamichi
AU - Nakano, Masahiro
AU - Pena Alvarez, Miriam
AU - Lopez Navarrete, Juan T
AU - Gomez-Garcia, Carlos J.
AU - Kertesz, Miklos
AU - Takimiya, Kazuo
AU - Casado, Juan
PY - 2016/11/14
Y1 - 2016/11/14
N2 - 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.
AB - 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.
U2 - 10.1002/anie.201605997
DO - 10.1002/anie.201605997
M3 - Article
JO - Angewandte Chemie International Edition
JF - Angewandte Chemie International Edition
SN - 1433-7851
ER -