Chameleonic layered metal-organic frameworks with variable charge-ordered states triggered by temperature and guest molecules

Jian Chen; Yoshihiro Sekine; Atsushi Okazawa; Hiroyasu Sato; Wataru Kosaka; Hitoshi Miyasaka

doi:10.1039/d0sc00684j

Chameleonic layered metal-organic frameworks with variable charge-ordered states triggered by temperature and guest molecules

Jian Chen, Yoshihiro Sekine, Atsushi Okazawa, Hiroyasu Sato, Wataru Kosaka, Hitoshi Miyasaka^*

^*Corresponding author for this work

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

19 Citations (Scopus)

Abstract

Molecular materials whose electronic states are multiply varied depending on external stimuli are among the most promising targets for the development of multiply accessible molecular switches. Here, we report a honeycomb layer composed of tetraoxolene-bridged iron (Fe) subunits whose charge-ordered states are multiply variable via thermal treatments and solvation/desolvation with the crystallinity intact. The compound is (NPr₄)₂[Fe₂(Cl₂An)₃] (1-d; NPr₄⁺ = tetra-n-propylammonium; Cl₂An^2- = 2,5-dichloro-3,6-dihydroxo-1,4-benzoquinonate), which possesses three charge-ordered states: A low-temperature (LT) phase [(Fe³⁺)₂(Cl₂An^2-)(Cl₂An^3-)₂]^2-; an intermediate (IM) phase [(Fe^2.5+)₂(Cl₂An^2-)(Cl₂An^2.5-)₂]^2-; and a high-temperature (HT) phase [(Fe²⁺)₂(Cl₂An^2-)₃]^2- that varies according to temperature. In addition, the LT phase of 1-d is reversibly changeable to another IM phase in its solvated compound 1via a solvation/desolvation process at room temperature. This example demonstrates a new multiple-switching system based on electron transfer and host-guest chemistry in a charge-flexible metal-organic framework.

Original language	English
Pages (from-to)	3610-3618
Number of pages	9
Journal	Chemical Science
Volume	11
Issue number	14
DOIs	https://doi.org/10.1039/d0sc00684j
Publication status	Published - 2020 Apr 14
Externally published	Yes

ASJC Scopus subject areas

Chemistry(all)

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@article{6a6c0410f02f48f0a57c0132f4899f17,

title = "Chameleonic layered metal-organic frameworks with variable charge-ordered states triggered by temperature and guest molecules",

abstract = "Molecular materials whose electronic states are multiply varied depending on external stimuli are among the most promising targets for the development of multiply accessible molecular switches. Here, we report a honeycomb layer composed of tetraoxolene-bridged iron (Fe) subunits whose charge-ordered states are multiply variable via thermal treatments and solvation/desolvation with the crystallinity intact. The compound is (NPr4)2[Fe2(Cl2An)3] (1-d; NPr4+ = tetra-n-propylammonium; Cl2An2- = 2,5-dichloro-3,6-dihydroxo-1,4-benzoquinonate), which possesses three charge-ordered states: A low-temperature (LT) phase [(Fe3+)2(Cl2An2-)(Cl2An3-)2]2-; an intermediate (IM) phase [(Fe2.5+)2(Cl2An2-)(Cl2An2.5-)2]2-; and a high-temperature (HT) phase [(Fe2+)2(Cl2An2-)3]2- that varies according to temperature. In addition, the LT phase of 1-d is reversibly changeable to another IM phase in its solvated compound 1via a solvation/desolvation process at room temperature. This example demonstrates a new multiple-switching system based on electron transfer and host-guest chemistry in a charge-flexible metal-organic framework.",

author = "Jian Chen and Yoshihiro Sekine and Atsushi Okazawa and Hiroyasu Sato and Wataru Kosaka and Hitoshi Miyasaka",

note = "Funding Information: The authors thank Prof. S. Hayami (Kumamoto University) for the helpful discussions on 57Fe M{\"o}ssbauer spectra and Dr K. Sugimoto (JASRI) for the SC-XRD measurements for the IM phase using a synchrotron beam at Spring-8. This work was supported by a Grant-in-Aid for Scientic Research (No. 16H02269, 18K19050, 18K05055, and 18H05208) from MEXT, Japan, and on Innovative Areas (“p-System Figuration” Area 2601, No. 17H05137) from the Japan Society for the Promotion of Science (JSPS), Japan, and the E-IMR project. Y. S. is thankful for nancial support received from the TOBE MAKI Scholarship Foundation and the Shorai Foundation for Science and Technology. J. C. gratefully acknowledges the nancial support received from the Chinese Scholarship Council (CSC) and the Institute for Materials Research, Tohoku University. Publisher Copyright: This journal is {\textcopyright} The Royal Society of Chemistry.",

year = "2020",

month = apr,

day = "14",

doi = "10.1039/d0sc00684j",

language = "English",

volume = "11",

pages = "3610--3618",

journal = "Chemical Science",

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publisher = "Royal Society of Chemistry",

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T1 - Chameleonic layered metal-organic frameworks with variable charge-ordered states triggered by temperature and guest molecules

AU - Chen, Jian

AU - Sekine, Yoshihiro

AU - Okazawa, Atsushi

AU - Sato, Hiroyasu

AU - Kosaka, Wataru

AU - Miyasaka, Hitoshi

N1 - Funding Information: The authors thank Prof. S. Hayami (Kumamoto University) for the helpful discussions on 57Fe Mössbauer spectra and Dr K. Sugimoto (JASRI) for the SC-XRD measurements for the IM phase using a synchrotron beam at Spring-8. This work was supported by a Grant-in-Aid for Scientic Research (No. 16H02269, 18K19050, 18K05055, and 18H05208) from MEXT, Japan, and on Innovative Areas (“p-System Figuration” Area 2601, No. 17H05137) from the Japan Society for the Promotion of Science (JSPS), Japan, and the E-IMR project. Y. S. is thankful for nancial support received from the TOBE MAKI Scholarship Foundation and the Shorai Foundation for Science and Technology. J. C. gratefully acknowledges the nancial support received from the Chinese Scholarship Council (CSC) and the Institute for Materials Research, Tohoku University. Publisher Copyright: This journal is © The Royal Society of Chemistry.

PY - 2020/4/14

Y1 - 2020/4/14

N2 - Molecular materials whose electronic states are multiply varied depending on external stimuli are among the most promising targets for the development of multiply accessible molecular switches. Here, we report a honeycomb layer composed of tetraoxolene-bridged iron (Fe) subunits whose charge-ordered states are multiply variable via thermal treatments and solvation/desolvation with the crystallinity intact. The compound is (NPr4)2[Fe2(Cl2An)3] (1-d; NPr4+ = tetra-n-propylammonium; Cl2An2- = 2,5-dichloro-3,6-dihydroxo-1,4-benzoquinonate), which possesses three charge-ordered states: A low-temperature (LT) phase [(Fe3+)2(Cl2An2-)(Cl2An3-)2]2-; an intermediate (IM) phase [(Fe2.5+)2(Cl2An2-)(Cl2An2.5-)2]2-; and a high-temperature (HT) phase [(Fe2+)2(Cl2An2-)3]2- that varies according to temperature. In addition, the LT phase of 1-d is reversibly changeable to another IM phase in its solvated compound 1via a solvation/desolvation process at room temperature. This example demonstrates a new multiple-switching system based on electron transfer and host-guest chemistry in a charge-flexible metal-organic framework.

AB - Molecular materials whose electronic states are multiply varied depending on external stimuli are among the most promising targets for the development of multiply accessible molecular switches. Here, we report a honeycomb layer composed of tetraoxolene-bridged iron (Fe) subunits whose charge-ordered states are multiply variable via thermal treatments and solvation/desolvation with the crystallinity intact. The compound is (NPr4)2[Fe2(Cl2An)3] (1-d; NPr4+ = tetra-n-propylammonium; Cl2An2- = 2,5-dichloro-3,6-dihydroxo-1,4-benzoquinonate), which possesses three charge-ordered states: A low-temperature (LT) phase [(Fe3+)2(Cl2An2-)(Cl2An3-)2]2-; an intermediate (IM) phase [(Fe2.5+)2(Cl2An2-)(Cl2An2.5-)2]2-; and a high-temperature (HT) phase [(Fe2+)2(Cl2An2-)3]2- that varies according to temperature. In addition, the LT phase of 1-d is reversibly changeable to another IM phase in its solvated compound 1via a solvation/desolvation process at room temperature. This example demonstrates a new multiple-switching system based on electron transfer and host-guest chemistry in a charge-flexible metal-organic framework.

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ER -

Chameleonic layered metal-organic frameworks with variable charge-ordered states triggered by temperature and guest molecules

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