6533b7d3fe1ef96bd1260a44
RESEARCH PRODUCT
Reversible Dimerization and Polymerization of a Janus Diradical To Produce Labile C−C Bonds and Large Chromic Effects
Naoyuki YanaiLili QiuMiklos KerteszJuan CasadoCarlos J. Gómez-garcíaMiriam Peña AlvarezMasahiro NakanoJuan T. López NavarreteJosé L. ZafraKazuo TakimiyaTakamichi MoriTakamichi Morisubject
Reaction mechanismChemistryDiradical010405 organic chemistrySupramolecular chemistryGeneral ChemistryGeneral MedicinePhotochemistry010402 general chemistry01 natural sciencesCatalysisReversible reaction0104 chemical scienceschemistry.chemical_compoundMonomerPolymerizationCovalent bondCyclophanedescription
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.
| year | journal | country | edition | language |
|---|---|---|---|---|
| 2016-10-26 | Angewandte Chemie |