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Introducing Selenium in Single-Component Molecular Conductors Based on Nickel Bis(dithiolene) Complexes.

Hadi Hachem1, HengBo Cui2, Reizo Kato2

  • 1Institut des Sciences Chimiques de Rennes, Université de Rennes, CNRS, UMR 6226, F-35000 Rennes, France.

Inorganic Chemistry
|May 21, 2021
PubMed
Summary
This summary is machine-generated.

Researchers synthesized two selenium-containing molecular conductors, [Ni(Et-thiazSedt)2] and [Ni(Et-thiazds)2]. The first shows unique dimer formation and low conductivity, while the second exhibits 1D electronic structure and pressure-sensitive conductivity.

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Area of Science:

  • Materials Science
  • Solid-State Chemistry
  • Molecular Electronics

Background:

  • Single-component molecular conductors offer tunable electronic properties.
  • Nickel dithiolene complexes are a well-studied class of molecular conductors.
  • Introducing chalcogen atoms (sulfur, selenium) can significantly alter material properties.

Purpose of the Study:

  • To synthesize and characterize selenated analogues of the molecular conductor [Ni(Et-thiazdt)2].
  • To investigate the impact of selenium incorporation on solid-state structure and electronic properties.
  • To explore the pressure-dependent conductivity of the novel selenated complexes.

Main Methods:

  • Chemical synthesis of novel nickel diselenolene and selenone complexes.
  • Single-crystal X-ray diffraction for structural analysis.
  • Electrical conductivity measurements under varying pressure conditions.
  • Band structure calculations using computational methods.

Main Results:

  • [Ni(Et-thiazSedt)2] exhibits unprecedented eclipsed dimer formation with short Se---Se contacts, leading to semiconducting behavior (σRT = 1.7 × 10⁻⁵ S cm⁻¹).
  • [Ni(Et-thiazds)2] forms layered structures with 1D electronic characteristics and a small HOMO-LUMO gap.
  • Conductivity of [Ni(Et-thiazds)2] increases by four orders of magnitude under 19 GPa, with a phase transition around 10 GPa.

Conclusions:

  • Selenium incorporation leads to distinct structural motifs and electronic properties compared to sulfur analogues.
  • The pressure-induced conductivity changes in [Ni(Et-thiazds)2] highlight its potential for pressure-responsive electronic devices.
  • These findings expand the scope of molecular conductors with tailored electronic and structural characteristics.