Structures and electrical conductivities of cation radical salts based on unsymmetrical [Au(III)(C-N)(S-S)] type dithiolate complexes

Kazuya Kubo, Akiko Nakao, Yasuyuki Ishii, Reizo Kato, Gen Etsu Matsubayashi

Research output: Contribution to journalArticle

6 Citations (Scopus)

Abstract

Crystals of [Au(ppy)(S-S)]2[Q][Solvent]n [ppy - = C-deprotonated-2-phenylpyridine(-); S-S = C8H 4S82-: 2-{(4,5-ethylenedithio)-l,3- dithiole-2-ylidene}-l,3-dihtiole-4,5-dithiolate(2-), C8H 4S6O22-: 2-{(4,5-ethylenedioxy)-l,3-dithiole-2-ylidene(-l,3-dihtiole-4,5-dithiolate (2-) ; Q = PF6-, BF4- AsF 6- and TaF6-; solvent = PhCl and PhCN; n = 0-0.5] type cation radical salts were prepared by constant current electrolysis of benzonitrile or chlorobenzene solutions of unsymmetrical [Au(ppy)(S-S)] type metal complexes with [Bun4N][Q] as electrolyte. These salts exhibit two types of unique columnar structures. The one (S-S = C8H4S82-, Q = PF 6-/S-S = C8H4S6O 22-, Q = BF4-) contains the two-fold head-to-head stacking of cation radicals while the other (S-S = C 8H4S82-, Q = AsF6 -, TaF6-) is based on the stacking of tetramers of cation radicals. [Au(ppy)(C8H4S 8)]2[PF6] shows semiconductive behavior (E a = 0.03 eV) under ambient pressure. Interestingly, it shows metallic behavior under high pressure (>0.8 GPa). To our knowledge, this is the first example of the metallic cation radical salt based on the unsymmetrical metal complex. Other radical cation salts show insulating or semiconducting behavior (Ea = 0.11-0.15 eV).

Original languageEnglish
Pages (from-to)425-428
Number of pages4
JournalSynthetic Metals
Volume153
Issue number1-3
DOIs
Publication statusPublished - 2005 Sep 21
Externally publishedYes

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Cations
Salts
Positive ions
salts
cations
conductivity
electrical resistivity
Coordination Complexes
Metal complexes
chlorobenzenes
electrolysis
Electrolysis
metals
Electrolytes
Electric Conductivity
electrolytes
Crystals
crystals

Keywords

  • Electrocrystallization
  • Elemental analysis
  • Organic conductors based on radical cation salts
  • Single-crystal growth
  • X-ray diffraction

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Materials Chemistry
  • Polymers and Plastics

Cite this

Structures and electrical conductivities of cation radical salts based on unsymmetrical [Au(III)(C-N)(S-S)] type dithiolate complexes. / Kubo, Kazuya; Nakao, Akiko; Ishii, Yasuyuki; Kato, Reizo; Matsubayashi, Gen Etsu.

In: Synthetic Metals, Vol. 153, No. 1-3, 21.09.2005, p. 425-428.

Research output: Contribution to journalArticle

Kubo, Kazuya ; Nakao, Akiko ; Ishii, Yasuyuki ; Kato, Reizo ; Matsubayashi, Gen Etsu. / Structures and electrical conductivities of cation radical salts based on unsymmetrical [Au(III)(C-N)(S-S)] type dithiolate complexes. In: Synthetic Metals. 2005 ; Vol. 153, No. 1-3. pp. 425-428.
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abstract = "Crystals of [Au(ppy)(S-S)]2[Q][Solvent]n [ppy - = C-deprotonated-2-phenylpyridine(-); S-S = C8H 4S82-: 2-{(4,5-ethylenedithio)-l,3- dithiole-2-ylidene}-l,3-dihtiole-4,5-dithiolate(2-), C8H 4S6O22-: 2-{(4,5-ethylenedioxy)-l,3-dithiole-2-ylidene(-l,3-dihtiole-4,5-dithiolate (2-) ; Q = PF6-, BF4- AsF 6- and TaF6-; solvent = PhCl and PhCN; n = 0-0.5] type cation radical salts were prepared by constant current electrolysis of benzonitrile or chlorobenzene solutions of unsymmetrical [Au(ppy)(S-S)] type metal complexes with [Bun4N][Q] as electrolyte. These salts exhibit two types of unique columnar structures. The one (S-S = C8H4S82-, Q = PF 6-/S-S = C8H4S6O 22-, Q = BF4-) contains the two-fold head-to-head stacking of cation radicals while the other (S-S = C 8H4S82-, Q = AsF6 -, TaF6-) is based on the stacking of tetramers of cation radicals. [Au(ppy)(C8H4S 8)]2[PF6] shows semiconductive behavior (E a = 0.03 eV) under ambient pressure. Interestingly, it shows metallic behavior under high pressure (>0.8 GPa). To our knowledge, this is the first example of the metallic cation radical salt based on the unsymmetrical metal complex. Other radical cation salts show insulating or semiconducting behavior (Ea = 0.11-0.15 eV).",
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T1 - Structures and electrical conductivities of cation radical salts based on unsymmetrical [Au(III)(C-N)(S-S)] type dithiolate complexes

AU - Kubo, Kazuya

AU - Nakao, Akiko

AU - Ishii, Yasuyuki

AU - Kato, Reizo

AU - Matsubayashi, Gen Etsu

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N2 - Crystals of [Au(ppy)(S-S)]2[Q][Solvent]n [ppy - = C-deprotonated-2-phenylpyridine(-); S-S = C8H 4S82-: 2-{(4,5-ethylenedithio)-l,3- dithiole-2-ylidene}-l,3-dihtiole-4,5-dithiolate(2-), C8H 4S6O22-: 2-{(4,5-ethylenedioxy)-l,3-dithiole-2-ylidene(-l,3-dihtiole-4,5-dithiolate (2-) ; Q = PF6-, BF4- AsF 6- and TaF6-; solvent = PhCl and PhCN; n = 0-0.5] type cation radical salts were prepared by constant current electrolysis of benzonitrile or chlorobenzene solutions of unsymmetrical [Au(ppy)(S-S)] type metal complexes with [Bun4N][Q] as electrolyte. These salts exhibit two types of unique columnar structures. The one (S-S = C8H4S82-, Q = PF 6-/S-S = C8H4S6O 22-, Q = BF4-) contains the two-fold head-to-head stacking of cation radicals while the other (S-S = C 8H4S82-, Q = AsF6 -, TaF6-) is based on the stacking of tetramers of cation radicals. [Au(ppy)(C8H4S 8)]2[PF6] shows semiconductive behavior (E a = 0.03 eV) under ambient pressure. Interestingly, it shows metallic behavior under high pressure (>0.8 GPa). To our knowledge, this is the first example of the metallic cation radical salt based on the unsymmetrical metal complex. Other radical cation salts show insulating or semiconducting behavior (Ea = 0.11-0.15 eV).

AB - Crystals of [Au(ppy)(S-S)]2[Q][Solvent]n [ppy - = C-deprotonated-2-phenylpyridine(-); S-S = C8H 4S82-: 2-{(4,5-ethylenedithio)-l,3- dithiole-2-ylidene}-l,3-dihtiole-4,5-dithiolate(2-), C8H 4S6O22-: 2-{(4,5-ethylenedioxy)-l,3-dithiole-2-ylidene(-l,3-dihtiole-4,5-dithiolate (2-) ; Q = PF6-, BF4- AsF 6- and TaF6-; solvent = PhCl and PhCN; n = 0-0.5] type cation radical salts were prepared by constant current electrolysis of benzonitrile or chlorobenzene solutions of unsymmetrical [Au(ppy)(S-S)] type metal complexes with [Bun4N][Q] as electrolyte. These salts exhibit two types of unique columnar structures. The one (S-S = C8H4S82-, Q = PF 6-/S-S = C8H4S6O 22-, Q = BF4-) contains the two-fold head-to-head stacking of cation radicals while the other (S-S = C 8H4S82-, Q = AsF6 -, TaF6-) is based on the stacking of tetramers of cation radicals. [Au(ppy)(C8H4S 8)]2[PF6] shows semiconductive behavior (E a = 0.03 eV) under ambient pressure. Interestingly, it shows metallic behavior under high pressure (>0.8 GPa). To our knowledge, this is the first example of the metallic cation radical salt based on the unsymmetrical metal complex. Other radical cation salts show insulating or semiconducting behavior (Ea = 0.11-0.15 eV).

KW - Electrocrystallization

KW - Elemental analysis

KW - Organic conductors based on radical cation salts

KW - Single-crystal growth

KW - X-ray diffraction

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