Organic Polyradicals as Redox Mediators: Effect of Intramolecular Radical Interactions on Their Efficiency
16 February 2021

The spin–spin interactions between unpaired electrons in organic (poly)radicals, especially nitroxides, are largely investigated and are of crucial importance for their applications in areas such as organic magnetism, molecular charge transfer, or multiple spin labeling in structural biology. Recently, 2,2,6,6-tetramethylpiperidinyloxyl and polymers functionalized with nitroxides have been described as successful redox mediators in several electrochemical applications; however, the study of spin–spin interaction effect in such an area is absent.

This communication reports the preparation of a novel family of discrete polynitroxide molecules, with the same number of radical units but different arrangements to study the effect of intramolecular spin–spin interactions on their electrochemical potential and their use as oxidation redox mediators in a Li–oxygen battery. We find that the intensity of interactions, as measured by the d1/d electron paramagnetic resonance parameter, progressively lowers the reduction potential. This allows us to tune the charging potential of the battery, optimizing its energy efficiency.

Hits: 633
Tuneable and low cost molecular electronics

Organic Polyradicals as Redox Mediators: Effect of Intramolecular Radical Interactions on Their Efficiency

Elena Badetti*, Vega Lloveras, Emanuele Amadio, Rosalia Di Lorenzo, Mara Olivares-Marín, Alvaro Y. Tesio, Songbai Zhang, Fangfang Pan, Kari Rissanen, Jaume Veciana, Dino Tonti*, Jose Vidal-Gancedo*, Cristiano Zonta, and Giulia Licini*

ACS Appl. Mater. Interfaces 2020, 12, 41, 45968–45975
Publication Date:September 15, 2020

Also at ICMAB

  • From high quality packing to disordered nucleation or phase separation in donor/acceptor interfaces: ClAlPc-C60 on Au(111)

    03 September 2021 183 hit(s) Molecular
    The dramatic consequences that the orientation adopted by the molecular dipoles, in diverse arrays of chloroaluminum phthalocyanine (ClAlPc) on Au(111), have on the ulterior adsorption and growth of C60 are explored by means of an all scanning probe microscopy approach. The unidirectional downwards organization of the molecular dipoles at the first layer reduces charge transfer from the metal to C60. Imbalance between attractive and repulsive interactions of the fullerenes are crucial for their ordered supramolecular aggregation.
  • Synthesis of 2D Porous Crystalline Materials in Simulated Microgravity

    27 August 2021 243 hit(s) Molecular
    To date, crystallization studies conducted in space laboratories, which are prohibitively costly and unsuitable to most research laboratories, have shown the valuable effects of microgravity during crystal growth and morphogenesis. Herein, an easy and highly efficient method is shown to achieve space-like experimentation conditions on Earth employing custom-made microfluidic devices to fabricate 2D porous crystalline molecular frameworks.
  • Rich Polymorphism of Layered NbS3

    20 August 2021 261 hit(s) Molecular
    Layered group V transition-metal trichalcogenides are paradigmatic low-dimensional materials providing an ever increasing series of unusual properties. They are all based on the same basic building units, one-dimensional MX3 (M = Nb, Ta; X = S, Se) trigonal-prismatic chains that condense into layers, but their electronic structures exhibit significant differences leading to a broad spectrum of transport properties, ranging from metals with one, two, or three charge density wave instabilities to semimetals with potential topological properties or semiconductors.
  • Red light-emitting Carborane-BODIPY dyes: Synthesis and properties of visible-light tuned fluorophores with enhanced boron content

    17 August 2021 281 hit(s) Molecular
    A small library of 2,6- and 3,5-distyrenyl-substituted carborane-BODIPY dyes was efficiently synthesized by means of a Pd-catalyzed Heck coupling reaction. Styrenyl-carborane derivatives were exploited as molecular tools to insert two carborane clusters into the fluorophore core and to extend the π-conjugation of the final molecule in a single synthetic step.
  • A Trapezoidal Octacyanoquinoid Acceptor Forms Solution and Surface Products by Antiparallel Shape Fitting with Conformational Dipole Momentum Switch

    06 August 2021 296 hit(s) Molecular
    A new compound formed by two antiparallelly disposed tetracyano thienoquinoidal units has been synthesized and studied by electrochemistry and several spectroscopic techniques. Its self-assembly on a Au(111) surface has been investigated by scanning tunneling microscopy.

INSTITUT DE CIÈNCIA DE MATERIALS DE BARCELONA, Copyright © 2020 ICMAB-CSIC | Privacy Policy | This email address is being protected from spambots. You need JavaScript enabled to view it.