Electrocrystallization, X-ray structure and electronic properties of the dmit-based salt [MePh3P] [Ni(dmit)2]3

Anthony E. Pullen; Hsiang Lin Liu; D. B. Tanner; Khalil A. Abboud; John R. Reynolds

doi:10.1039/a606026i

Electrocrystallization, X-ray structure and electronic properties of the dmit-based salt [MePh₃P] [Ni(dmit)₂]₃

Anthony E. Pullen, Hsiang Lin Liu, D. B. Tanner, Khalil A. Abboud, John R. Reynolds^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

12 Citations (Scopus)

Abstract

Electrooxidation of [Ni(dmit)₂]^-(dmit = C₃S₅^2- = 4,5-dithiolate-2-thione-1,3-dithiole) in 3:1 acetonitrile-acetone at a Pt wire anode in the presence of methyltriphenylphosphonium bromide electrolyte yields the radical anion salt complex [MePh₃P][Ni(dmit)₂]₃. Black shiny platelet crystals were harvested. They belong to the monoclinic space group P2₁/c, M = 1631.41, a = 21.0872(1), b = 17.4930(2), c = 15.7203(2) Å, β = 107.072(1)°, V = 5543.4(1) Å³ and Z=4. The crystal packing structure consists of columns of Ni(dmit)₂ units of width one unit separated by columns of MePh₃P⁺ counter-ions. The Ni(dmit)₂ columns are composed of dimers of Ni(dmit)₂ units with non-bonding interactions with six other pairs of Ni(dmit)₂ units. The arrangement of the dimers with respect to each other in the columns has been seen in other phosphonium-based Ni(dmit)₂ complexes and is similar to the packing of κ-BEDT-TTF radical cation salts which have shown superconductivity. Single-crystal temperature-dependent conductivity measurements have shown that this material is semiconducting with a room-temperature conductivity of 0.1 S cm^-1 and a thermal activation energy of 0.22 eV.

Original language	English
Pages (from-to)	377-380
Number of pages	4
Journal	Journal of Materials Chemistry
Volume	7
Issue number	3
DOIs	https://doi.org/10.1039/a606026i
Publication status	Published - 1997 Mar
Externally published	Yes

ASJC Scopus subject areas

General Chemistry
Materials Chemistry

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@article{77617d61d7c540b2b6bb357f78b3fb7e,

title = "Electrocrystallization, X-ray structure and electronic properties of the dmit-based salt [MePh3P] [Ni(dmit)2]3",

abstract = "Electrooxidation of [Ni(dmit)2]-(dmit = C3S52- = 4,5-dithiolate-2-thione-1,3-dithiole) in 3:1 acetonitrile-acetone at a Pt wire anode in the presence of methyltriphenylphosphonium bromide electrolyte yields the radical anion salt complex [MePh3P][Ni(dmit)2]3. Black shiny platelet crystals were harvested. They belong to the monoclinic space group P21/c, M = 1631.41, a = 21.0872(1), b = 17.4930(2), c = 15.7203(2) {\AA}, β = 107.072(1)°, V = 5543.4(1) {\AA}3 and Z=4. The crystal packing structure consists of columns of Ni(dmit)2 units of width one unit separated by columns of MePh3P+ counter-ions. The Ni(dmit)2 columns are composed of dimers of Ni(dmit)2 units with non-bonding interactions with six other pairs of Ni(dmit)2 units. The arrangement of the dimers with respect to each other in the columns has been seen in other phosphonium-based Ni(dmit)2 complexes and is similar to the packing of κ-BEDT-TTF radical cation salts which have shown superconductivity. Single-crystal temperature-dependent conductivity measurements have shown that this material is semiconducting with a room-temperature conductivity of 0.1 S cm-1 and a thermal activation energy of 0.22 eV.",

author = "Pullen, {Anthony E.} and Liu, {Hsiang Lin} and Tanner, {D. B.} and Abboud, {Khalil A.} and Reynolds, {John R.}",

year = "1997",

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doi = "10.1039/a606026i",

language = "English",

volume = "7",

pages = "377--380",

journal = "Journal of Materials Chemistry",

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T1 - Electrocrystallization, X-ray structure and electronic properties of the dmit-based salt [MePh3P] [Ni(dmit)2]3

AU - Pullen, Anthony E.

AU - Liu, Hsiang Lin

AU - Tanner, D. B.

AU - Abboud, Khalil A.

AU - Reynolds, John R.

PY - 1997/3

Y1 - 1997/3

N2 - Electrooxidation of [Ni(dmit)2]-(dmit = C3S52- = 4,5-dithiolate-2-thione-1,3-dithiole) in 3:1 acetonitrile-acetone at a Pt wire anode in the presence of methyltriphenylphosphonium bromide electrolyte yields the radical anion salt complex [MePh3P][Ni(dmit)2]3. Black shiny platelet crystals were harvested. They belong to the monoclinic space group P21/c, M = 1631.41, a = 21.0872(1), b = 17.4930(2), c = 15.7203(2) Å, β = 107.072(1)°, V = 5543.4(1) Å3 and Z=4. The crystal packing structure consists of columns of Ni(dmit)2 units of width one unit separated by columns of MePh3P+ counter-ions. The Ni(dmit)2 columns are composed of dimers of Ni(dmit)2 units with non-bonding interactions with six other pairs of Ni(dmit)2 units. The arrangement of the dimers with respect to each other in the columns has been seen in other phosphonium-based Ni(dmit)2 complexes and is similar to the packing of κ-BEDT-TTF radical cation salts which have shown superconductivity. Single-crystal temperature-dependent conductivity measurements have shown that this material is semiconducting with a room-temperature conductivity of 0.1 S cm-1 and a thermal activation energy of 0.22 eV.

AB - Electrooxidation of [Ni(dmit)2]-(dmit = C3S52- = 4,5-dithiolate-2-thione-1,3-dithiole) in 3:1 acetonitrile-acetone at a Pt wire anode in the presence of methyltriphenylphosphonium bromide electrolyte yields the radical anion salt complex [MePh3P][Ni(dmit)2]3. Black shiny platelet crystals were harvested. They belong to the monoclinic space group P21/c, M = 1631.41, a = 21.0872(1), b = 17.4930(2), c = 15.7203(2) Å, β = 107.072(1)°, V = 5543.4(1) Å3 and Z=4. The crystal packing structure consists of columns of Ni(dmit)2 units of width one unit separated by columns of MePh3P+ counter-ions. The Ni(dmit)2 columns are composed of dimers of Ni(dmit)2 units with non-bonding interactions with six other pairs of Ni(dmit)2 units. The arrangement of the dimers with respect to each other in the columns has been seen in other phosphonium-based Ni(dmit)2 complexes and is similar to the packing of κ-BEDT-TTF radical cation salts which have shown superconductivity. Single-crystal temperature-dependent conductivity measurements have shown that this material is semiconducting with a room-temperature conductivity of 0.1 S cm-1 and a thermal activation energy of 0.22 eV.

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Electrocrystallization, X-ray structure and electronic properties of the dmit-based salt [MePh₃P] [Ni(dmit)₂]₃

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