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Title: | Localization versus Delocalization in Chiral Single Component Conductors of Gold Bis(dithiolene) Complexes |
Author: | Branzea, Diana G. Pop, Flavia Auban-Senzier, Pascale Clerac, Rodolphe Alemany i Cahner, Pere Canadell, Enric, 1950- Avarvari, Narcis |
Keywords: | Complexos metàl·lics Química de l'estat sòlid Conductivitat elèctrica Ciència dels materials Metal complexes Solid state chemistry Electric conductivity Materials science |
Issue Date: | 1-Jun-2016 |
Publisher: | American Chemical Society |
Abstract: | The first examples of chiral single component conductors are reported. Both (S,S) and (R,R) enantiomers of 5,6-dimethy1-5,6-dihydro-1,4-dithiin-2,3-dithiolate (dm=dddt) ligand have been used to prepare anionic metal bis(dithiOlene) complexes formulated as ([(n-Bu)(4)N][M(dm-dddt)(2)] (M = Au, Ni), which are isostructural according to single crystal X-ray analysis. Single crystal transport measurements indicate semiconducting behavior for the anionic radical Ni complexes, with low room temperature conductivity values and high activation energies. Electrocrystallization experiments provided neutral [M(dm-dddt)(2)] (M = Au, Ni) complexes. The neutral radical gold compounds Show intermolecular S center dot center dot center dot S inte'raction's in the solid state giving rise to layers interconnected through Weak C-H center dot center dot center dot S hydrogen bonds. The most peculiar structural feature concerns a dissymmetry between the two dithiolene moieties, while the nickel counterpart is symmetric. Single crystal resistivity measurements show thermally activated behavior for the open-shell gold complexes, with room temperature conductivity values of 0.02-0:04 S.cm-' and activation energies strongly influenced by hydrostatic pressure. A thorough thebretical study on nickel anion radical and gold neutral radiCal bis(dithiolene) complexes applied to the chiral complexes [M(dm-dddt)(2)] (M = Ail, Ni-) and to a series of previously reported compounds addressed, the issue of symmetry versus asymmetry from an electronic coupling perspective between the two dithiolene ligands. It results that neutral gold' complexes with dithiolene ligands without 'extended delocalization are Class II mixed-valent compounds in the Robin and Day classification, presenting an inherent tendency toward asymmetric structures,, which can be however modulated by the intermolecular organization in the solid state. |
Note: | Versió postprint del document publicat a: https://doi.org/10.1021/jacs.6b03342 |
It is part of: | Journal of the American Chemical Society, 2016, vol. 138, num. 21, p. 6838-6851 |
URI: | http://hdl.handle.net/2445/128163 |
Related resource: | https://doi.org/10.1021/jacs.6b03342 |
ISSN: | 0002-7863 |
Appears in Collections: | Articles publicats en revistes (Ciència dels Materials i Química Física) Articles publicats en revistes (Institut de Química Teòrica i Computacional (IQTCUB)) |
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