Mixed-valence gold bis(diselenolene) complex turning metallic under pressure
While oxidation of d8 anionic gold bis(dithiolene) complexes most often affords the corresponding neutral radical single-component conductor, an original gold bis(diselenolene) complex isolated as a Ph4P+ salt affords upon electrocrystallization a mixed-valence 1 : 2 salt, [Ph4P][Au(Me-thiazds)2]2 (...
| Autores: | , , , , , , , , |
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| Tipo de recurso: | artículo |
| Estado: | Versión aceptada para publicación |
| Fecha de publicación: | 2021 |
| País: | España |
| Institución: | Consejo Superior de Investigaciones Científicas (CSIC) |
| Repositorio: | DIGITAL.CSIC. Repositorio Institucional del CSIC |
| OAI Identifier: | oai:digital.csic.es:10261/251110 |
| Acceso en línea: | http://hdl.handle.net/10261/251110 |
| Access Level: | acceso abierto |
| Palabra clave: | Single-component conductors Hydrogen-bonding interaction Dithiolene complexes |
| Sumario: | While oxidation of d8 anionic gold bis(dithiolene) complexes most often affords the corresponding neutral radical single-component conductor, an original gold bis(diselenolene) complex isolated as a Ph4P+ salt affords upon electrocrystallization a mixed-valence 1 : 2 salt, [Ph4P][Au(Me-thiazds)2]2 (Me-thiazds: 2-methyl-1,3-thiazoline-2-thione-4,5-diselenolate). This salt exhibits a rare charge alternation associated with the simultaneous presence of both cis and trans isomers of the gold complex in the conducting layers. The salt is semiconducting (σRT = 3 × 10−2 S cm−1, Eact = 0.137 eV) but, in contrast with other 1 : 2 gold bis(dithiolene) salts, turns metallic under pressure (>10 GPa). [Ph4P][Au(Me-thiazds)2]2 is thus the first metallic, fully characterized, 1 : 2 mixed-valence gold complex, opening the door for the preparation of highly conducting solids of this type. |
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