Solid-state electrochemistry of a semiconducting MMX-type diplatinum iodide chain complex

Hiroaki Iguchi; Ayman Nafady; Shinya Takaishi; Masahiro Yamashita; Alan M. Bond

doi:10.1021/ic402980t

Solid-state electrochemistry of a semiconducting MMX-type diplatinum iodide chain complex

Hiroaki Iguchi, Ayman Nafady, Shinya Takaishi, Masahiro Yamashita, Alan M. Bond

SCI - Chemistry

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

6 Citations (Scopus)

Abstract

Electron-transfer-facilitated dissolution, ion insertion, and desorption associated with an MMX-type quasi-one-dimensional iodide-bridged dinuclear Pt complex (MMX chain) have been investigated for the first time. K ₂(NC₃N)[Pt₂(pop)₄I]·4H ₂O (1) (NC₃N²⁺ = (H₃NC ₃H₆NH₃)²⁺; pop = P₂H ₂O₅^2-) is a semiconductor with a three-dimensional coordination-bond and hydrogen-bond network included in the chain. The cyclic voltammetry of 1 was studied by using 1-modified electrodes in contact with acetonitrile solutions containing electrolyte. The chemical reversibility for oxidation of 1 depended on the electrolyte cation size, with large cations such as tetrabutylammonium (Bu₄N⁺) being too large to penetrate the pores formed by the loss of K⁺ and NC ₃N²⁺ upon oxidation. The potential for reduction of 1 decreased as the cation size increased. The presence of the acid induced additional well-defined processes but with gradual solid dissolution, attributed to the breaking of the coordination-bond networks.

Original language	English
Pages (from-to)	4022-4028
Number of pages	7
Journal	Inorganic Chemistry
Volume	53
Issue number	8
DOIs	https://doi.org/10.1021/ic402980t
Publication status	Published - 2014 Apr 21

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title = "Solid-state electrochemistry of a semiconducting MMX-type diplatinum iodide chain complex",

abstract = "Electron-transfer-facilitated dissolution, ion insertion, and desorption associated with an MMX-type quasi-one-dimensional iodide-bridged dinuclear Pt complex (MMX chain) have been investigated for the first time. K 2(NC3N)[Pt2(pop)4I]·4H 2O (1) (NC3N2+ = (H3NC 3H6NH3)2+; pop = P2H 2O52-) is a semiconductor with a three-dimensional coordination-bond and hydrogen-bond network included in the chain. The cyclic voltammetry of 1 was studied by using 1-modified electrodes in contact with acetonitrile solutions containing electrolyte. The chemical reversibility for oxidation of 1 depended on the electrolyte cation size, with large cations such as tetrabutylammonium (Bu4N+) being too large to penetrate the pores formed by the loss of K+ and NC 3N2+ upon oxidation. The potential for reduction of 1 decreased as the cation size increased. The presence of the acid induced additional well-defined processes but with gradual solid dissolution, attributed to the breaking of the coordination-bond networks.",

author = "Hiroaki Iguchi and Ayman Nafady and Shinya Takaishi and Masahiro Yamashita and Bond, {Alan M.}",

year = "2014",

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doi = "10.1021/ic402980t",

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T1 - Solid-state electrochemistry of a semiconducting MMX-type diplatinum iodide chain complex

AU - Iguchi, Hiroaki

AU - Nafady, Ayman

AU - Takaishi, Shinya

AU - Yamashita, Masahiro

AU - Bond, Alan M.

PY - 2014/4/21

Y1 - 2014/4/21

N2 - Electron-transfer-facilitated dissolution, ion insertion, and desorption associated with an MMX-type quasi-one-dimensional iodide-bridged dinuclear Pt complex (MMX chain) have been investigated for the first time. K 2(NC3N)[Pt2(pop)4I]·4H 2O (1) (NC3N2+ = (H3NC 3H6NH3)2+; pop = P2H 2O52-) is a semiconductor with a three-dimensional coordination-bond and hydrogen-bond network included in the chain. The cyclic voltammetry of 1 was studied by using 1-modified electrodes in contact with acetonitrile solutions containing electrolyte. The chemical reversibility for oxidation of 1 depended on the electrolyte cation size, with large cations such as tetrabutylammonium (Bu4N+) being too large to penetrate the pores formed by the loss of K+ and NC 3N2+ upon oxidation. The potential for reduction of 1 decreased as the cation size increased. The presence of the acid induced additional well-defined processes but with gradual solid dissolution, attributed to the breaking of the coordination-bond networks.

AB - Electron-transfer-facilitated dissolution, ion insertion, and desorption associated with an MMX-type quasi-one-dimensional iodide-bridged dinuclear Pt complex (MMX chain) have been investigated for the first time. K 2(NC3N)[Pt2(pop)4I]·4H 2O (1) (NC3N2+ = (H3NC 3H6NH3)2+; pop = P2H 2O52-) is a semiconductor with a three-dimensional coordination-bond and hydrogen-bond network included in the chain. The cyclic voltammetry of 1 was studied by using 1-modified electrodes in contact with acetonitrile solutions containing electrolyte. The chemical reversibility for oxidation of 1 depended on the electrolyte cation size, with large cations such as tetrabutylammonium (Bu4N+) being too large to penetrate the pores formed by the loss of K+ and NC 3N2+ upon oxidation. The potential for reduction of 1 decreased as the cation size increased. The presence of the acid induced additional well-defined processes but with gradual solid dissolution, attributed to the breaking of the coordination-bond networks.

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DO - 10.1021/ic402980t

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AN - SCOPUS:84899462104

SN - 0020-1669

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SP - 4022

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JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 8

ER -

Solid-state electrochemistry of a semiconducting MMX-type diplatinum iodide chain complex

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