Continuous control of optical gaps in quasi-one-dimensional bromide-bridged platinum complexes by utilizing chemical pressure

Shohei Kumagai; Hiroaki Iguchi; Shinya Takaishi; Brian K. Breedlove; Masahiro Yamashita; Hiroyuki Matsuzaki; Hiroshi Okamoto; Kenichi Kato; Masaki Takata

doi:10.1021/ic502071u

Continuous control of optical gaps in quasi-one-dimensional bromide-bridged platinum complexes by utilizing chemical pressure

Shohei Kumagai, Hiroaki Iguchi, Shinya Takaishi, Brian K. Breedlove, Masahiro Yamashita, Hiroyuki Matsuzaki, Hiroshi Okamoto, Kenichi Kato, Masaki Takata

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

9 Citations (Scopus)

Abstract

The optical gap in a series of bromo-bridged platinum chain complexes, [Pt(en)₂Br](C_n-Y)₂·H₂O (en = ethylenediamine; C_n-Y = dialkyl sulfosuccinate; n = the number of carbon atoms), was controlled by using chemical pressure. From the single-crystal structure, [Pt(en)₂Br](C₆-Y)₂·H₂O is in a mixed-valence state at 200 K. In addition, Pt-Pt distances decreased with an increase in n or with a decrease in the temperature. Continuous decreases in the optical gaps upon cooling were observed for n = 5, 7. The smallest gap of 1.20 eV was observed for n = 7 at 50 K. For n = 12, the complex was still in a mixed-valence state at 5 K, although the Pt-Pt distance was quite short. This is probably because of the energetic mismatch between 5dz₂ orbitals of the Pt ions and 4p_z orbitals of the Br ions.

Original language	English
Pages (from-to)	11764-11769
Number of pages	6
Journal	Inorganic chemistry
Volume	53
Issue number	21
DOIs	https://doi.org/10.1021/ic502071u
Publication status	Published - 2014 Nov 3

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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@article{8134b4ad09fb44229c9355a66b1019ee,

title = "Continuous control of optical gaps in quasi-one-dimensional bromide-bridged platinum complexes by utilizing chemical pressure",

abstract = "The optical gap in a series of bromo-bridged platinum chain complexes, [Pt(en)2Br](Cn-Y)2·H2O (en = ethylenediamine; Cn-Y = dialkyl sulfosuccinate; n = the number of carbon atoms), was controlled by using chemical pressure. From the single-crystal structure, [Pt(en)2Br](C6-Y)2·H2O is in a mixed-valence state at 200 K. In addition, Pt-Pt distances decreased with an increase in n or with a decrease in the temperature. Continuous decreases in the optical gaps upon cooling were observed for n = 5, 7. The smallest gap of 1.20 eV was observed for n = 7 at 50 K. For n = 12, the complex was still in a mixed-valence state at 5 K, although the Pt-Pt distance was quite short. This is probably because of the energetic mismatch between 5dz2 orbitals of the Pt ions and 4pz orbitals of the Br ions.",

author = "Shohei Kumagai and Hiroaki Iguchi and Shinya Takaishi and Breedlove, {Brian K.} and Masahiro Yamashita and Hiroyuki Matsuzaki and Hiroshi Okamoto and Kenichi Kato and Masaki Takata",

note = "Publisher Copyright: {\textcopyright} 2014 American Chemical Society.",

year = "2014",

month = nov,

day = "3",

doi = "10.1021/ic502071u",

language = "English",

volume = "53",

pages = "11764--11769",

journal = "Inorganic Chemistry",

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T1 - Continuous control of optical gaps in quasi-one-dimensional bromide-bridged platinum complexes by utilizing chemical pressure

AU - Kumagai, Shohei

AU - Iguchi, Hiroaki

AU - Takaishi, Shinya

AU - Breedlove, Brian K.

AU - Yamashita, Masahiro

AU - Matsuzaki, Hiroyuki

AU - Okamoto, Hiroshi

AU - Kato, Kenichi

AU - Takata, Masaki

PY - 2014/11/3

Y1 - 2014/11/3

N2 - The optical gap in a series of bromo-bridged platinum chain complexes, [Pt(en)2Br](Cn-Y)2·H2O (en = ethylenediamine; Cn-Y = dialkyl sulfosuccinate; n = the number of carbon atoms), was controlled by using chemical pressure. From the single-crystal structure, [Pt(en)2Br](C6-Y)2·H2O is in a mixed-valence state at 200 K. In addition, Pt-Pt distances decreased with an increase in n or with a decrease in the temperature. Continuous decreases in the optical gaps upon cooling were observed for n = 5, 7. The smallest gap of 1.20 eV was observed for n = 7 at 50 K. For n = 12, the complex was still in a mixed-valence state at 5 K, although the Pt-Pt distance was quite short. This is probably because of the energetic mismatch between 5dz2 orbitals of the Pt ions and 4pz orbitals of the Br ions.

AB - The optical gap in a series of bromo-bridged platinum chain complexes, [Pt(en)2Br](Cn-Y)2·H2O (en = ethylenediamine; Cn-Y = dialkyl sulfosuccinate; n = the number of carbon atoms), was controlled by using chemical pressure. From the single-crystal structure, [Pt(en)2Br](C6-Y)2·H2O is in a mixed-valence state at 200 K. In addition, Pt-Pt distances decreased with an increase in n or with a decrease in the temperature. Continuous decreases in the optical gaps upon cooling were observed for n = 5, 7. The smallest gap of 1.20 eV was observed for n = 7 at 50 K. For n = 12, the complex was still in a mixed-valence state at 5 K, although the Pt-Pt distance was quite short. This is probably because of the energetic mismatch between 5dz2 orbitals of the Pt ions and 4pz orbitals of the Br ions.

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DO - 10.1021/ic502071u

M3 - Article

AN - SCOPUS:84908609023

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JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 21

ER -

Continuous control of optical gaps in quasi-one-dimensional bromide-bridged platinum complexes by utilizing chemical pressure

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