Smallest Optical Gap for Pt(II)-Pt(IV) Mixed-Valence Pt-Cl and Pt-Br Chain Complexes Achieved by Using a Multiple-Hydrogen-Bond Approach

M. Rasel Mian; H. Iguchi; S. Takaishi; U. Afrin; T. Miyamoto; H. Okamoto; Masahiro Yamashita

doi:10.1021/acs.inorgchem.8b01910

Smallest Optical Gap for Pt(II)-Pt(IV) Mixed-Valence Pt-Cl and Pt-Br Chain Complexes Achieved by Using a Multiple-Hydrogen-Bond Approach

M. Rasel Mian, H. Iguchi, S. Takaishi, U. Afrin, T. Miyamoto, H. Okamoto, Masahiro Yamashita

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Abstract

A multiple-hydrogen-bond approach was applied to shorten Pt-X-Pt distances in Cl- and Br-bridged Pt chain complexes. [Pt(dabdOH) ₂ Cl]Cl ₂ (5) and [Pt(dabdOH) ₂ Br]Br ₂ (6) (dabdOH = (2S,3S)-2,3-diaminobutane-1,4-diol) contain hydroxy groups, which form additional hydrogen bonds with counteranions. 5 has the shortest Pt-Cl-Pt distance (5.0747(8) Å) of all Cl-bridged Pt chain complexes reported to date. Furthermore, the smallest optical gap (1.45 eV for 5 and 1.19 eV for 6) in any Cl- or Br-bridged Pt chain complex was achieved. 6 has the highest electrical conductivity (1.9 × 10 ^-5 S cm ^-1 at room temperature) of all Br-bridged Pt chain complexes. This study shows that the introduction of additional hydrogen bonds between the ligands and halides is effective to enhance the electronic properties of halogen-bridged metal complexes.

Original language	English
Pages (from-to)	114-120
Number of pages	7
Journal	Inorganic chemistry
Volume	58
Issue number	1
DOIs	https://doi.org/10.1021/acs.inorgchem.8b01910
Publication status	Published - 2019 Jan 7

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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@article{6e44e24c42a64c4baf5eefddac9793bd,

title = "Smallest Optical Gap for Pt(II)-Pt(IV) Mixed-Valence Pt-Cl and Pt-Br Chain Complexes Achieved by Using a Multiple-Hydrogen-Bond Approach",

abstract = " A multiple-hydrogen-bond approach was applied to shorten Pt-X-Pt distances in Cl- and Br-bridged Pt chain complexes. [Pt(dabdOH) 2 Cl]Cl 2 (5) and [Pt(dabdOH) 2 Br]Br 2 (6) (dabdOH = (2S,3S)-2,3-diaminobutane-1,4-diol) contain hydroxy groups, which form additional hydrogen bonds with counteranions. 5 has the shortest Pt-Cl-Pt distance (5.0747(8) {\AA}) of all Cl-bridged Pt chain complexes reported to date. Furthermore, the smallest optical gap (1.45 eV for 5 and 1.19 eV for 6) in any Cl- or Br-bridged Pt chain complex was achieved. 6 has the highest electrical conductivity (1.9 × 10 -5 S cm -1 at room temperature) of all Br-bridged Pt chain complexes. This study shows that the introduction of additional hydrogen bonds between the ligands and halides is effective to enhance the electronic properties of halogen-bridged metal complexes. ",

author = "Mian, {M. Rasel} and H. Iguchi and S. Takaishi and U. Afrin and T. Miyamoto and H. Okamoto and Masahiro Yamashita",

note = "Funding Information: This work was partly supported by JSPS KAKENHI grant numbers JP15K17828 (H.I.), JP18K14233 (H.I.), JP18H04498 (H.I.), JP18H01166 (H.O.), and JP26248015 (M.Y.), the Sumitomo Foundation (H.I.), the CASIO Science Promotion Foundation (H.I.), the Ogasawara Foundation for the Promotion of Science and Engineering (H.I.), the Program for Interdisciplinary Research in Tohoku University Frontier Research Institute for Interdisciplinary Sciences (H.I.), and CREST, JST (H.I., M.Y., and H.O.). M.Y. thanks the support by the 111 project (B18030) from China. We thank Prof. Brian K. Breedlove for his support on writing. Publisher Copyright: {\textcopyright} 2018 American Chemical Society.",

year = "2019",

month = jan,

day = "7",

doi = "10.1021/acs.inorgchem.8b01910",

language = "English",

volume = "58",

pages = "114--120",

journal = "Inorganic Chemistry",

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T1 - Smallest Optical Gap for Pt(II)-Pt(IV) Mixed-Valence Pt-Cl and Pt-Br Chain Complexes Achieved by Using a Multiple-Hydrogen-Bond Approach

AU - Mian, M. Rasel

AU - Iguchi, H.

AU - Takaishi, S.

AU - Afrin, U.

AU - Miyamoto, T.

AU - Okamoto, H.

AU - Yamashita, Masahiro

N1 - Funding Information: This work was partly supported by JSPS KAKENHI grant numbers JP15K17828 (H.I.), JP18K14233 (H.I.), JP18H04498 (H.I.), JP18H01166 (H.O.), and JP26248015 (M.Y.), the Sumitomo Foundation (H.I.), the CASIO Science Promotion Foundation (H.I.), the Ogasawara Foundation for the Promotion of Science and Engineering (H.I.), the Program for Interdisciplinary Research in Tohoku University Frontier Research Institute for Interdisciplinary Sciences (H.I.), and CREST, JST (H.I., M.Y., and H.O.). M.Y. thanks the support by the 111 project (B18030) from China. We thank Prof. Brian K. Breedlove for his support on writing. Publisher Copyright: © 2018 American Chemical Society.

PY - 2019/1/7

Y1 - 2019/1/7

N2 - A multiple-hydrogen-bond approach was applied to shorten Pt-X-Pt distances in Cl- and Br-bridged Pt chain complexes. [Pt(dabdOH) 2 Cl]Cl 2 (5) and [Pt(dabdOH) 2 Br]Br 2 (6) (dabdOH = (2S,3S)-2,3-diaminobutane-1,4-diol) contain hydroxy groups, which form additional hydrogen bonds with counteranions. 5 has the shortest Pt-Cl-Pt distance (5.0747(8) Å) of all Cl-bridged Pt chain complexes reported to date. Furthermore, the smallest optical gap (1.45 eV for 5 and 1.19 eV for 6) in any Cl- or Br-bridged Pt chain complex was achieved. 6 has the highest electrical conductivity (1.9 × 10 -5 S cm -1 at room temperature) of all Br-bridged Pt chain complexes. This study shows that the introduction of additional hydrogen bonds between the ligands and halides is effective to enhance the electronic properties of halogen-bridged metal complexes.

AB - A multiple-hydrogen-bond approach was applied to shorten Pt-X-Pt distances in Cl- and Br-bridged Pt chain complexes. [Pt(dabdOH) 2 Cl]Cl 2 (5) and [Pt(dabdOH) 2 Br]Br 2 (6) (dabdOH = (2S,3S)-2,3-diaminobutane-1,4-diol) contain hydroxy groups, which form additional hydrogen bonds with counteranions. 5 has the shortest Pt-Cl-Pt distance (5.0747(8) Å) of all Cl-bridged Pt chain complexes reported to date. Furthermore, the smallest optical gap (1.45 eV for 5 and 1.19 eV for 6) in any Cl- or Br-bridged Pt chain complex was achieved. 6 has the highest electrical conductivity (1.9 × 10 -5 S cm -1 at room temperature) of all Br-bridged Pt chain complexes. This study shows that the introduction of additional hydrogen bonds between the ligands and halides is effective to enhance the electronic properties of halogen-bridged metal complexes.

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U2 - 10.1021/acs.inorgchem.8b01910

DO - 10.1021/acs.inorgchem.8b01910

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VL - 58

SP - 114

EP - 120

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 1

ER -

Smallest Optical Gap for Pt(II)-Pt(IV) Mixed-Valence Pt-Cl and Pt-Br Chain Complexes Achieved by Using a Multiple-Hydrogen-Bond Approach

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