希土類フタロシアニンを介した金ナノ粒子間の量子伝導制御

• Project Area: Fusion Materials: Creative Development of Materials and Exploration of Their Function through Molecular Control
• Project/Area Number: 23107502
• Research Category: Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: Hokkaido University
• Principal Investigator: 中村 貴義 北海道大学, 電子科学研究所, 教授 (60270790)
• Project Period (FY): 2011-04-01 – 2013-03-31
• Project Status: Completed (Fiscal Year 2012)
• Budget Amount: ¥5,980,000 (Direct Cost: ¥4,600,000、Indirect Cost: ¥1,380,000); Fiscal Year 2012: ¥2,990,000 (Direct Cost: ¥2,300,000、Indirect Cost: ¥690,000); Fiscal Year 2011: ¥2,990,000 (Direct Cost: ¥2,300,000、Indirect Cost: ¥690,000)
• Keywords: 希土類フタロシアニン / 単分子磁石 / 量子伝導 / 金ナノ粒子 / 無機－有機複合構造 / 無機有機複合体 / 磁性

Outline of Annual Research Achievements

本研究は金ナノ粒子－有機分子複合構造の電気－磁気物性評価を通じて、デバイス応用へ向けた基礎的なデータを得、その基盤を形成することを目的とした。具体的には、希土類イオンの種類により、強磁性、単分子磁性など様々な磁性を発現する希土類フタロシアニン錯体と金ナノ粒子をファンデルワールス相互作用を介して集積化した集積構造において、金ナノ粒子の帯電効果に伴うトンネル電子の生成と、有機分子の電気－磁気構造との相関に基づく多様な物性発現を目指した。電子－磁気構造と強く相関したトンネル伝導電子が示す量子物性を探究し、その機序を解明するとともに、強磁場下での輸送特性評価等を通じて、磁気構造と強く相関したトンネル伝導電子に基づく機能を開拓することを目指し、研究を進めた。その結果、
１．Lu, Tbなどを中心金属とする平均粒径約4 nm の単分散ナノ粒子で形成された集積体をファンデルワールス相互作用によって安定化することに成功した。
２．いずれの集積体においても、フタロシアニンは単分子吸着をしており、特にTbの場合は単分子磁石が分散した構造を持つことを明らかにした。
３．Lu錯体において低温でのCollective Tunnelingを実現することができ、またTB錯体の場合には、トンネル電子とf電子スピンとの相関を伺わせる結果が得られた。
以上の様に、希土類フタロシアニン錯体－金ナノ粒子集積体は興味深い量子伝導性を示しており、今後、電子デバイス等への応用に向けた基盤として重要な知見が得られた。

Research Progress Status

24年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

24年度が最終年度であるため、記入しない。

Research Products

• [Journal Article] Molecular Motion in Pyridazinium/Crown Ether Supramolecular Cation Salts of a Nickel Dithiolene Complex (2013)
  • Author(s): Zun-qi Liu, Li Lin, Kazuya Kubo, Nirihisa Hoshino, Shin-ichiro Noro, Tomoyuki Akutagawa,* Takayoshi Nakamura
  • Journal Title: Dalton Transactions Volume: 42 Issue: 8 Pages: 2930-2939
  • DOI: 10.1039/c2dt32542j
  • NAID: 120005350087
  • Peer Reviewed
• [Journal Article] (3-Fluoro-4-methoxy-anilinium+)([18]Crown-6) Supramolecular Cation Salt of Ferromagnetic [MnIICrIII (oxalate)3] (2013)
  • Author(s): Toru Endo, Kazuya Kubo, Masashi Yoshitake, Shin-ichiro Noro, Tomoyuki Akutagawa, and Takayoshi Nakamura
  • Journal Title: Chemistry Letters Volume: 42 Issue: 2 Pages: 137-139
  • DOI: 10.1246/cl.2013.137
  • NAID: 130004426850
  • Peer Reviewed
• [Journal Article] Crystal Structures and Magnetic Properties of (4,4'-Phenylazophenyl)-diammonium(Crown ethers)[Ni(dmit)2]2 Crystals (2012)
  • Author(s): Norihisa Hoshino, Kazuya Kubo, Takayoshi Nakamura, and Tomoyuki Akutagawa
  • Journal Title: Dalton Transactions Volume: 41 Issue: 31 Pages: 12968-12975
  • DOI: 10.1039/c2dt30807j
  • Peer Reviewed
• [Journal Article] Cation-Anion Packing and Molecular Motion in (m-Fluoroanilinium)(dibenzo[18]crown-6)[Ni(mnt)2]-(CH3CN)0.25 Crystals (2012)
  • Author(s): Kiyonori Takahashi, Norihisa Hoshino, Kazuya Kubo, Takayoshi Nakamura, Tomoyuki Akutagawa
  • Journal Title: CrystEngComm. Volume: 14 Issue: 16 Pages: 5235-5241
  • DOI: 10.1039/c2ce25493j
  • Peer Reviewed
• [Journal Article] Incorporation of Cationic Electron Donor of Ni-pyridyltetrathiafulvalene with Anionic Electron Acceptor of Polyoxometalate (2012)
  • Author(s): Ryo Tsunashima, Takumi Matsumoto, Kei Kondo, Yoshihiko Suyama, Yukihiro Nishioka, Jun Kawamata, Shin-ichiro Noro, Takayoshi Nakamura, Tomoyuki Akutagawa , Katsuya Ishiguro
  • Journal Title: Dalton Transactions. Volume: 41 Issue: 33 Pages: 10060-10064
  • DOI: 10.1039/c2dt30398a
  • Peer Reviewed
• [Journal Article] Synthesis and Crystal Structure of a One-dimensional Cu(II) Coordination Polymer Bridged by Inorganic CH3SO3- Anions Using Werner-type Cu(II) Complexes as Building Blocks (2012)
  • Author(s): S. Noro, K. Kubo and T. Nakamura
  • Journal Title: Chem. Lett. 41 Volume: 41 Issue: 8 Pages: 772-773
  • DOI: 10.1246/cl.2012.772
  • NAID: 130004426636
  • Peer Reviewed
• [Journal Article] Flexible cis-Cyclohexane-1,4-diammonium in Magnetic [Ni(dmit)_2] Crystals (2012)
  • Author(s): Qiong Ye, Ping-Ping Shi, Zi-Qi Chen, Tomoyuki Akutagawa, Shin-ichiro Noro, Takayoshi Nakamura
  • Journal Title: European Journal of Inorganic Chemistry Volume: (未定)(印刷中) Issue: 23 Pages: 3732-3739
  • DOI: 10.1002/ejic.201200099
  • Peer Reviewed
• [Journal Article] Synthesis, Crystal Structure, and Adsorption Properties of Werner-type Cu(II) Complex [Cu(CF3SO3)2(4-methylpyridine)4] (2012)
  • Author(s): S. Noro, K. Fukuhara, K. Kubo and T. Nakamura
  • Journal Title: Chem. Lett. Volume: 41 Issue: 10 Pages: 1314-1316
  • DOI: 10.1246/cl.2012.1314
  • NAID: 130004426366
  • Peer Reviewed
• [Journal Article] Supramolecular Rotators of (Aniliniums)([18]crown-6) in Electrically Conducting [Ni(dmit)2] Crystals, (2012)
  • Author(s): Norihisa Hoshino, Yuuya Yoshii, Kazuya Kubo, Masaki Aonuma, Takayoshi Nakamura, Tomoyuki Akutagawa
  • Journal Title: Inorganic Chemistr Volume: 51 Issue: 23 Pages: 12968-12975
  • DOI: 10.1021/ic302093b
  • Peer Reviewed
• [Journal Article] Structural Phase Transition Induced by Molecular Motions within a (Anilinium)(L-Tartarate) Ionic Molecular Crystal (2012)
  • Author(s): Yuuya Yoshii, Norihisa Hoshino, Takayoshi Nakamura, Tomoyuki Akutagawa
  • Journal Title: CrystEngComm. Volume: 14 Issue: 21 Pages: 7458-7465
  • DOI: 10.1039/c2ce25945a
  • Peer Reviewed
• [Journal Article] Highly Selective CO2 Adsorption Accompanied with Low-Energy Regeneration in a Two-Dimensional CU(II) Porous Coordination Polymer with Inorganic Fluoriuated PF6- Anions (2012)
  • Author(s): S. Noro, T. Fukushima, S. Kitagawa, T. Nakamura, 他
  • Journal Title: Inorg. Chem. Volume: 52 Issue: 1 Pages: 280-285
  • DOI: 10.1021/ic301823j
  • Peer Reviewed
• [Journal Article] Supramolecular cations of the m-fluoroanilinium(dibenzo[18]crown-6) in ferromagnetic salt (2011)
  • Author(s): Toru Endo, Tomoyuki Akutagawa, Shin-ichiro Noro, Takayoshi Nakamura
  • Journal Title: Dalton Transaction Volume: 40 Issue: 7 Pages: 1491-1496
  • DOI: 10.1039/c0dt01140a
  • Peer Reviewed
• [Journal Article] An Imidazolate- and Azide-Bridged Copper (II) Coordination Polymer Consisting of Alternating Di- and Mononuclear Units (2011)
  • Author(s): Ken-ichi Sakai, Tomoyuki Akutagawa, Takayoshi Nakamura
  • Journal Title: Eur.J.Inorg.Chem. Volume: 2011 Issue: 1 Pages: 116-120
  • DOI: 10.1002/ejic.201000835
  • Peer Reviewed
• [Journal Article] Diverse structures and adsorption properties of quasi-Werner-type copper (II) complexes (2011)
  • Author(s): Shin-ichiro Noro, Tomonori Ohba, Katsuo Fukuhara, Yukiko Takahashi, Tomoyuki Akutagawa, Takayoshi Nakamura
  • Journal Title: Dalton Transactions Volume: 40 Issue: 10 Pages: 2268-2274
  • DOI: 10.1039/c0dt01129k
  • Peer Reviewed
• [Journal Article] Exploring the Thermochromism of Sulfite-embedded Polyoxometalate Capsules (2011)
  • Author(s): Ryo Tsunashima, De Liang Long, Toru Endo, Shin-ichiro Noro, Tomoyuki Akutagawa, Takayoshi Nakamura, Raul Quesada Cabrera, Paul F.McMillan, Paul Kogerler, Leroy Cronin
  • Journal Title: Phys.Chem.Chem.Phys. Volume: 13 Issue: 16 Pages: 7295-7297
  • DOI: 10.1039/c1cp20074g
  • Peer Reviewed
• [Journal Article] Rational Construction of Wide Coordination Space and Control of Adsorption Properties in One-Dimensional Cu(II) Coordination Polymer (2011)
  • Author(s): S.Noro, K.Fukuhara, K.Kubo, T.Nakamura
  • Journal Title: Crystal Growth & Design Volume: 11 Issue: 6 Pages: 2379-2385
  • DOI: 10.1021/cg2001392
  • Peer Reviewed
• [Journal Article] Hydrogen-bonded Assemblies of Two-Electron Reduced Mixed-Valence [XMo_<12>O_<40>] (X=P and Si) with p-Phenylenediamines (2011)
  • Author(s): Tomoyuki Akutagawa, Fumito Kudo, Ryo Tsunashima, Shin-ichiro Noro; Leroy Cronin, Takayoshi Nakamura
  • Journal Title: Inorganic Chemistry Volume: 50 Issue: 14 Pages: 6711-6718
  • DOI: 10.1021/ic200683e
  • Peer Reviewed
• [Journal Article] Polymornhs and-Structural Phase Transition of [Ni(dmit_2)]^-Crystals Induced by Flexible (trans-Cyclohexane-1,4-diammonium)(Benzo[18]crown-6)_2 Supramolecule (2011)
  • Author(s): Qiong Ye, Tomoyuki Akutagawa, Nonhisa Hoshino, Takemitsu Kikuchi, Shin-ichiro Noro, Ren Gen Xiong, Takayoshi Nakamura
  • Journal Title: Crystal Growth & Design Volume: 11 Issue: 9 Pages: 4175-4182
  • DOI: 10.1021/cg2007556
  • Peer Reviewed
• [Journal Article] 4-(cyanomethyl) anilinium Perchlorate : A New Displacive-Type Molecular Ferroelectric (2011)
  • Author(s): Hong-Ling Cai, Wen Zhang, Jia-Zhen Ge, Yi Zhang, Kunio Awaga, Takayoshi Nakamura, Ren Gen
  • Journal Title: Phys.Rev.Lett. Volume: 107 Issue: 14 Pages: 147-601
  • DOI: 10.1103/physrevlett.107.147601
  • NAID: 120006795654
  • Peer Reviewed
• [Journal Article] Structural Phase Transition Due to the Flexible Supramolecule of (4-cyanomethylanilinium) ([18]crown-6) in [Ni(dmit)2]-Crystal (2011)
  • Author(s): Qiong Ye, Tomoyuki Akutagawa, Heng Yun Ye, Tian Hang, Jia Zhen Ge, Ren-Gen Xiong, Shin-ichiro Noro, Takayoshi Nakamura
  • Journal Title: Cryst.Eng.Commun. Volume: 13 Issue: 20 Pages: 6185-6191
  • DOI: 10.1039/c1ce05581j
  • Peer Reviewed
• [Journal Article] Huge Dielectric Response and Molecular Motions in Paddle-Wheel [CuII2(Adamantylcarboxylate)4(DMF)2]・(DMF)2 (2011)
  • Author(s): Qiong Ye, Kiyonori Takahashi, Norihisa Hoshino, Takemitsu Kikuchi, Tomoyuki Akutagawa, Shin-ichiro Noro, Sadamu Takeda, Takayoshi Nakamura
  • Journal Title: Chem.Eur.J. Volume: 17 Issue: 51 Pages: 14442-14449
  • DOI: 10.1002/chem.201101743
  • Peer Reviewed
• [Presentation] Molecular Multiferroics Based on Supramolecular Rotators (2012)
  • Author(s): T. Nakamura, M. Yoshitake, K. Kubo and S. Noro
  • Organizer: 8th IUPAC International Conference on Novel Materials and their Synthesis (NMS-VIII) 22nd International Symposium on Fine Chemistry and Functional Polymers (FCFP-XXII)
  • Place of Presentation: 西北大学・西安・中国
  • Year and Date: 2012-10-14
  • Invited
• [Presentation] Organic-Inorganic Hybrid Systems toward "Dynamic" Functional Materials (2012)
  • Author(s): T.Nakamura
  • Organizer: 1st Discussion Symposium on 'Inorganic Biology and Protocells : Engineering Artificial Life'
  • Place of Presentation: University of Glasgow (UK)(招待講演)
  • Year and Date: 2012-09-13
• [Presentation] Ferroelectrics and Multiferroics based on Supramolecular Rotators (2011)
  • Author(s): T.Nakamura
  • Organizer: the third RIES-CIS Symposium
  • Place of Presentation: National Chiao Tung University (Taiwan)(招待講演)
  • Year and Date: 2011-10-28