Creation of Magnetic Ferroelectrics Based on Hydrogen-Bonded Benzosemiquinone Complexes
| Project/Area Number |
24550162
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Multi-year Fund |
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| Section | 一般 |
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| Research Field |
Functional materials chemistry
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| Research Institution | University of Hyogo |
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Principal Investigator |
MITSUMI Minoru 兵庫県立大学, 物質理学研究科, 助教 (20295752)
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| Project Period (FY) |
2012-04-01 – 2015-03-31
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| Project Status |
Completed (Fiscal Year 2014)
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| Budget Amount *help |
¥5,460,000 (Direct Cost: ¥4,200,000、Indirect Cost: ¥1,260,000)
Fiscal Year 2014: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
Fiscal Year 2013: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
Fiscal Year 2012: ¥2,860,000 (Direct Cost: ¥2,200,000、Indirect Cost: ¥660,000)
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| Keywords | セミキノン錯体 / プロトン秩序ー無秩序転移 / プロトンダイナミクス / 固体高分解能NMR / 誘電性 / 水素結合 / 固体高分解能 NMR / 強誘電体 / 秩序ー無秩序転移 / 秩序ー無秩序相転移 |
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| Outline of Final Research Achievements |
We have synthesized one-dimensional hydrogen-bonded rhodium(II)-η5-semiquinone complexes [Cp*Rh(η5-p-HQ-Me4)]X (X=PF6 (1), CF3SO3(2)) that exhibits a paraelectric-antiferroelectric second-order phase transition at 237.1 and 207.8 K, respectively. The 13C CP/MAS NMR spectra demonstrate that the proton is dynamically disordered in the RT phase. To maintain short-range protonic correlations, kink defects known as protonic solitons are expected to form topologically on the boundary of short-range order areas. The protonation/deprotonation of [Cp*Rh(η5-p-HQ-Me4)]+ led to hapticity changes of semiquinone ligand accompanied by reduction/oxidation by the π-bonded rhodium fragment, giving stable η6-hydroquinone and η4-benzoquinone complexes, respectively. Therefore, kink defects presumably consist of these stable η6- and η4-coordinated complexes. The generated protonic solitons migrate rapidly in the H-bonded chain through successive proton transfer coupled with electron transfer.
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Report
(4 results)
Research Products
(19 results)
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[Journal Article] Proton Order－Disorder Phenomena in a Hydrogen-Bonded Rhodium－η5-Semiquinone Complex: A Possible Dielectric Response Mechanism2015
Author(s)
Minoru Mitsumi, Kazunari Ezaki, Yuuki Komatsu, Koshiro Toriumi, Tatsuya Miyatou, Motohiro Mizuno, Nobuaki Azuma, Yuji Miyazaki, Motohiro Nakano, Yasutaka Kitagawa, Takayasu Hanashima, Ryoji Kiyanagi, Takashi Ohhara, and Kazuhiro Nakasuji
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Journal Title
Chemistry - A European Journal
Volume: 21
Issue: 27
Pages: 9682-9696
DOI
Related Report
Peer Reviewed / Acknowledgement Compliant
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[Journal Article] Bistable Multifunctionality and Switchable Strong Ferromagnetic-to-Anti ferromagnetic Coupling in a One-Dimen sional Rhodium(I)-Semiquinonato Complex2014
Author(s)
Mitsumi M., Nishitani T., Yamasaki S., Shimada N., Komatsu Y., Toriumi K., Kitagawa Y., Okumura M., Miyazaki Y., Gorska N., Inaba A., Kanda A., Hanasaki N
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Journal Title
J. Am. Chem. Soc
Volume: 136
Issue: 19
Pages: 7026-7037
DOI
Related Report
Peer Reviewed
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