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Article Dans Une Revue Chemistry - A European Journal Année : 2010

A Neutral Zwitterionic Molecular Solid

Abdelkrim El-Ghayoury
Cécile Mézière
Sergey Simonov
  • Fonction : Auteur
Leokadiya Zorina
  • Fonction : Auteur
Manuel Cobian
  • Fonction : Auteur
Enric Canadell
  • Fonction : Auteur
Carme Rovira
  • Fonction : Auteur
Bálint Náfrádi
  • Fonction : Auteur
Balázs Sipos
  • Fonction : Auteur
László Forró
  • Fonction : Auteur
Patrick Batail
  • Fonction : Auteur
  • PersonId : 992004

Résumé

We report on the acid ethylenedithiotetrathiafulvaleneamidoglycine (EDT-TTF-CO-NH-CH2-CO2H; 1; EDT-TTF=ethylenedithiotetrathiafulvalene) and the 1:1 adduct [(EDT-TTF).+-CO-NH-CH2-(CO2)−][(EDT-TTF)-CO-NH-CH2-(CO2H)]⋅CH3OH (2), a new type of hydrogen-bonded, 1:1 acid/zwitterion hybrid embrace of redox peptidics into a two-dimensional architecture, an example of a system deliberately fashioned so that oxidation of π-conjugated cores toward the radical-cation form would interfere with the activity of the appended ionizable residues in the presence of a templating base during crystal growth. First-principles calculations demonstrate that, notwithstanding preconceived ideas, a metallic state is more stable than the hole-localized alternatives for a neat 1:1 neutral acid/zwitterion hybrid. The inhomogeneous Coulomb field associated with proton-shared, interstacks O-H⋅⋅⋅O hydrogen bonds between the ionizable residues distributed on both sides of the two-dimensional π-conjugated framework leads, however, to a weak hole localization responsible for the activated but high conductivity of 1 S cm−1. This situation is reminiscent of the role of the environment on electron transfer in tetraheme cytochrome c, in which the protonation state of a heme propionate becomes paramount, or ion-gated transport phenomena in biology. These observations open rather intriguing opportunities for the construction of electronic systems at the interface of chemistry and biology.

Domaines

Chimie

Dates et versions

hal-01390631 , version 1 (02-11-2016)

Identifiants

Citer

Abdelkrim El-Ghayoury, Cécile Mézière, Sergey Simonov, Leokadiya Zorina, Manuel Cobian, et al.. A Neutral Zwitterionic Molecular Solid. Chemistry - A European Journal, 2010, 16 (47), pp.14051 - 14059. ⟨10.1002/chem.201001875⟩. ⟨hal-01390631⟩
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