Development and Functions of Dynamic Supramolecular Systems Coupled with Electronic Systems for Energy Conversion
| Project/Area Number |
16074201
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| Research Category |
Grant-in-Aid for Scientific Research on Priority Areas
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| Allocation Type | Single-year Grants |
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| Review Section |
Science and Engineering
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| Research Institution | Hokkaido University |
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Principal Investigator |
NAKAMURA Takayoshi Hokkaido University, Research Institute for Electronic Science, Professor (60270790)
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| Project Period (FY) |
2004 – 2007
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| Project Status |
Completed (Fiscal Year 2007)
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| Budget Amount *help |
¥16,200,000 (Direct Cost: ¥16,200,000)
Fiscal Year 2007: ¥4,400,000 (Direct Cost: ¥4,400,000)
Fiscal Year 2006: ¥4,400,000 (Direct Cost: ¥4,400,000)
Fiscal Year 2005: ¥4,400,000 (Direct Cost: ¥4,400,000)
Fiscal Year 2004: ¥3,000,000 (Direct Cost: ¥3,000,000)
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| Keywords | Metal complexes / Molecular Rotators / Ferroelectrics / Supramolecules / Crystal structure / Molecular magnetism / Molecular conductors / クラウンエーテル / イオン電動 / イオン電導 / イオン伝導 |
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| Research Abstract |
In this project, we aim at the developments of novel molecular systems based on molecular conductors and magnets with supramolecular cations having dynamic feature. As for the building blocks for molecular conductors and magnets, we are using [Ni (dmit) 2] and other metal complexes. Suplamoleclar structures based on crown ethers are combined with the complexes to form novel molecular systems. In this study, we mainly examined molecular rotator structures of organic ammonium and [18]crown-6 derivatives in [Ni (dmit) 2] salts.
We introduced -NH2 at o-position of the anilinium and synthesized (HOPD)+([18]crown-6) [Ni (dmit) 2] crystals. Strong dipole-dipole interaction induced the tight packing of cation layers, which prevented flip-flop motion of aryl rings. On the other hand, [18]crown-6 was rotating in the crystal as in the case of (PhNH3) ([18] crown-6) (Ni (dmit) 2).
We introduced -F and -NH2 at m-position of the anilinium and synthesized (HMFA)+(dibenzo[18]crown-6) [Ni (dmit) 2] and (HMPD)+(dibenzo [18] crown-6) [Ni (dmi1) 2] crystals. HMFA and HMPD salts gave the same composition and crystal structures.
Since HMFA and HMPD have dipole moments, it was possible to control the flip-flop motion of these molecular rotators by applying external electric field. It was proved that the crystal was the ferroelectrics with the Curie temperature of at around 350 K. Adamantylammonium was introduced in the supuramolecular structure instead of arylammonium derivatives. In the crystals, the rotation of adamantly group was maintained below 120 K, which was confirmed by 1H-NMR measurements.
In conclusion, we introduced supramolecular rotator structures in electronic active crystals, which is one of the key steps to realize highly efficient energy conversion systems. In addition, we could develop novel ferroelectrics based on molecular rotator structures.
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Report
(5 results)
Research Products
(55 results)
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[Journal Article] Diversities of Coordination Geometry at Cu2+ Center in the Bis(maleonitriledithiolato)cuprate Complexes : Syntheses, Magnetic Properties, X-ray Crystal Structural Analyses, and DFT Calcuations2006
Author(s)
X.M.Ren, Z.P.Ni, S.Noro, T.Akutagawa, S.Nishihara, T.Nakamura, Y.X.Sui, Y.Song
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Journal Title
Cryst. Gtowth ＆ Des 6
Pages: 2530-2537
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[Journal Article] Quai-one-dimentional molecular magnets based on derivatives of (fluorobenzyl) pyridinium with the [M(mnt)_2] monoanion (M=Ni, Pd or Pt; mnt(^<2->)=maleonitrileditiolate) : Syntheses, crystal structures and magnetic properties2006
Author(s)
X.Ren, S.Nishihara, T.Akutagawa, S.Noro, T.Nakamura, W.Fujita, K.Awaga, Z.Ni, J.Xie, Q.Meng, R.Kremer
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Journal Title
Dalton Transaction 16
Pages: 1988-1994
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[Journal Article] Molecular Rotor of Cs2([18]crown-6)3 in the Solid State Coupled with the Magnetism of [Ni(dmit)2]2005
Author(s)
T. Akutagawa, K. Shitagami, S. Nishihara, S. Takeda, T. Hasegawa, T. Nakamura, Y. Hosokoshi, K. Inoue, S. Ikeuchi, Y. Miyazaki, K. Saito
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Journal Title
J. Am. Chem. Soc. 127
Pages: 4397-4402
Description
「研究成果報告書概要(欧文)」より
Related Report
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[Journal Article] Molecular Rotor of Cs_2([18]crown-6)_3 in the Solid State Coupled with the Magnetism of [Ni(dmit)_2]2005
Author(s)
T.Akutagawa, K.Shitagami, S.Nishihara, S.Takeda, T.Hasegawa, T.Nakamura, Y.Hosokoshi, K.Inoue, S.Ikeuchi, Y.Miyazaki, K.Saito
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Journal Title
J.Am.Chem.Soc. 127
Pages: 4397-4402
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[Journal Article] Metal-Organic Thin-Film Transistor (MOTFT) Based on a Bis(o-diiminobenzosemiquinonate Nickel (II) Complex2005
Author(s)
S.Noro, H.C.Chang, T.Takenobu, Y.Murayama, T.Kanbara, T.Aoyama, T.Sassa, T.Wada, D.Tanaka, S.Kitagawa, Y.Iwasa, T.Akutagawa, T.Nakamura
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Journal Title
J.Am.Chem.Soc 127
Pages: 10012-10013
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