Anisotropic chemical pressure effects in single-component molecular metals based on radical dithiolene and diselenolene gold complexes. - Université de Rennes Accéder directement au contenu
Article Dans Une Revue Journal of the American Chemical Society Année : 2012

Anisotropic chemical pressure effects in single-component molecular metals based on radical dithiolene and diselenolene gold complexes.

Résumé

On the basis of the reported radical neutral complex [Au(Et-thiazdt)(2)] (Et-thiazdt = N-ethyl-1,3-thiazoline-2-thione-4,5-dithiolate), a series of single-component conductors derived from [Au(Et-thiazdt)(2)], also noted as [AuS(4)(═S)(2)], has been developed, by replacing the outer sulfur atoms of the thiazoline-2-thione rings by oxygen atoms and/or by replacing the coordinating sulfur atoms by selenium atoms toward the corresponding diselenolene complexes. Comparison of the X-ray crystal structures and transport properties of the four isostructural complexes, noted as [AuS(4)(═S)(2)], [AuS(4)(═O)(2)], [AuSe(4)(═S)(2)], and [AuSe(4)(═O)(2)], shows that the oxygen substitution on the outer thiazoline ring actually decreases the conductivity by a factor of 100, despite a contracted unit cell volume reflecting a positive chemical pressure effect. On the other hand, the S/Se substitution increases the conductivity by a factor of 100, and the pressure needed to transform these semiconductors into the metallic state is shifted from 13 kbar in [AuS(4)(═S)(2)] to only ≈6 kbar in [AuSe(4)(═S)(2)]. Analysis of unit cell evolutions and ab initio band structure calculations demonstrates the strongly anisotropic nature of this chemical pressure effect and provides an explanation for the observed changes in conductivity. The greater sensitivity of these neutral single-component conductors to external pressure, as compared with "classical" radical salts, is also highlighted.

Domaines

Matériaux
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Dates et versions

hal-00843771 , version 1 (12-07-2013)

Identifiants

Citer

Gilles Yzambart, Nathalie Bellec, Ghassan Nasser, Olivier Jeannin, Thierry Roisnel, et al.. Anisotropic chemical pressure effects in single-component molecular metals based on radical dithiolene and diselenolene gold complexes.. Journal of the American Chemical Society, 2012, 134 (41), pp.17138-48. ⟨10.1021/ja3065649⟩. ⟨hal-00843771⟩
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