Development of Coordination Polymer Spin Crossover Complexes with Optical Properties

• Project/Area Number: 15K05485
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Research Field: Functional solid state chemistry
• Research Institution: Toho University
• Principal Investigator: KITAZAWA Takafumi 東邦大学, 理学部, 教授 (60246767)
• Project Period (FY): 2015-04-01 – 2018-03-31
• Project Status: Completed (Fiscal Year 2017)
• Budget Amount: ¥5,070,000 (Direct Cost: ¥3,900,000、Indirect Cost: ¥1,170,000); Fiscal Year 2017: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000); Fiscal Year 2016: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000); Fiscal Year 2015: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000)
• Keywords: スピンクロスオーバー / 磁気物性 / 高スピン / 低スピン / 光物性 / ホスト構造 / ゲスト分子 / 超分子構造 / 高スピン錯体 / 低スピン錯体 / 高分子錯体 / 転移温度 / 結合距離 / 分子磁性 / 磁化率 / 親金相互作用 / 蛍光 / 超分子錯体 / 八面体錯体 / メスバウアー分光法

Outline of Final Research Achievements

We synthesized spin crossover complexes with insertedguest molecules; Fe[4-(3-pentyl)pyridine]2[Au(CN)2]2guest.The insertion of guest molecules enhances the chemical pressure in the two-dimensional Hofmann-type frameworks and promotes the SCO behavior depending on the size of guest molecules of
dichlorobenzene isomers. We found that the highest crossover temperature is achieved in the case of the shortest interlayer distance introducing the p-dichlorobenzene guest.We also have prepared the 2D spin crossover complexes
Fe(py)2Pd(CN)4 has been characterised by Mossbauer spectroscopic measurements, single crystal X-ray determination and SQUID measurements. The Mossbauer spectra indicate that the iron(II) spin states are in high spin states at 298 K and are in low spin states at 77 K.The delicate shifts might be associated with subtle balances between different vibrations around Fe(II) atoms and electronic factors. Five novel 3D cadmium(II) cyanide coordination polymers also were found.

Research Products

• [Journal Article] Synthesis and Crystal Structures of Cadmium(II) Cyanide with Branched-Butoxyethanol (2018)
  • Author(s): Takeshi Kawasaki, Takafumi Kitazawa
  • Journal Title: Crystals Volume: 8,221 Issue: 5 Pages: 1-10
  • DOI: 10.3390/cryst8050221
  • Peer Reviewed / Open Access
• [Journal Article] 双安定性を示すHofmann-like 高分子錯体 (2018)
  • Author(s): 北澤孝史、関谷円香、 高橋正
  • Journal Title: KURRI-EKR-22 (Reserach Reactor Institute, Kyoto University) Volume: 22 Pages: 40-44
  • Open Access
• [Journal Article] Guest molecule inserted spin crossover complexes: Fe[4-(3-pentyl)pyridine]2[Au(CN)2]2.Guest (2017)
  • Author(s): Yusuke Ueki, Jun Okabayashi, Takafumi Kitazawa
  • Journal Title: Chemistry Letters Volume: 46(5) Issue: 5 Pages: 747-749
  • DOI: 10.1246/cl.170149
  • NAID: 130005655716
  • Peer Reviewed
• [Journal Article] Spin crossover behaviour in Hofmann-like coordination polymer Fe(py)2[Pd(CN)4] with 57Fe Mossbauer spectra (2017)
  • Author(s): Kitazawa Takafumi、Kishida Takanori、Kawasaki Takeshi、Takahashi Masashi
  • Journal Title: Hyperfine Interactions Volume: 238 Issue: 1 Pages: 1-9
  • DOI: 10.1007/s10751-017-1436-4
  • Peer Reviewed / Open Access
• [Journal Article] Modification of Cooperativity and Critical Temperatures on a Hofmann-Like Template Structure by Modular Substituent (2017)
  • Author(s): Takashi Kosone ,Takeshi Kawasaki , Itaru Tomori , Jun Okabayashi, Takafumi Kitazawa
  • Journal Title: Inorganics Volume: 5,55 Issue: 3 Pages: 1-8
  • DOI: 10.3390/inorganics5030055
  • Peer Reviewed / Open Access
• [Journal Article] Ethyl Isonicotinate を配位子とするスピンクロスオーバー錯体 (2017)
  • Author(s): 椎名 瞳、高橋 正、北澤 孝史
  • Journal Title: KURRI-EKR-18(ISSN 2189-7107) Volume: 1 Pages: 4-7
  • Open Access / Acknowledgement Compliant
• [Journal Article] Emission Behaviour of a Series of Bimetallic Cd(II)-Au(I) Coordination Polymers (2016)
  • Author(s): Akihiko Yamagishi, Takeshi Kawasaki, Kei Hiruma, Hisako Sato,Takafumi Kitazawa
  • Journal Title: Dalton Trans. Volume: 45 Issue: 18 Pages: 7823-7828
  • DOI: 10.1039/c6dt00537c
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Mossbauer Spectroscopic Study on Hofmann-like Coordination Polymer Fe(4-Clpy)2[Ni(CN)4] (2016)
  • Author(s): Takafumi Kitazawa, Takeshi Kawasaki, Hitomi Shiina, Masashi Takahashi
  • Journal Title: Croat. Chem. Acta Volume: 89 Issue: 1 Pages: 111-115
  • DOI: 10.5562/cca2758
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Three-Dimensional Cadmium(II) Cyanide Coordination Polymers with Ethoxy-, Butoxy- and Hexyloxy-ehtanol (2016)
  • Author(s): Takeshi Kawasaki, Takafumi Kitazawa
  • Journal Title: Crystals Volume: 6 Issue: 9 Pages: 103-103
  • DOI: 10.3390/cryst6090103
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] 2D Spin-Crossover Coordination Polymer Fe(hexyl-nicotinate)2[Au(CN)2]2 (2016)
  • Author(s): Shoutaro Ueno, Takeshi Kawasaki, Jun Okabayashi, Takafumi Kitazawa
  • Journal Title: Bull. Chem. Soc. Jpn. Volume: 89 Issue: 5 Pages: 581-583
  • DOI: 10.1246/bcsj.20150411
  • NAID: 130005150881
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Guest-dependent spin transition with long range intermediate state for 2-dimensional Hofmann-like coordination polymer (2016)
  • Author(s): Takashi Kosone, Takafumi Kitazawa
  • Journal Title: Inorganic Chimica Acta Volume: 439 Pages: 159-163
  • DOI: 10.1016/j.ica.2015.10.011
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Ligand 4-X pyridine (X = Cl, Br, I) dependence in Hofmann-type spin Crossover complexes: Fe(4-Xpyridine)2[Au(CN)2]2 (2016)
  • Author(s): Jun Okabayashi, Shotaro Ueno, Takeshi Kawasaki, Takafumi Kitazawa
  • Journal Title: Inorganic Chimica Acta Volume: 445 Pages: 17-21
  • DOI: 10.1016/j.ica.2016.10.024
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Mossbauer spectroscopic study on spin crossover coordination polymer Fe(3-Clpy)2[Pd(CN)4] (2016)
  • Author(s): Takafumi Kitazawa, Madoka Sekiya, Takeshi Kawasaki, Masashi Takahashi
  • Journal Title: Hyperfine Interactions Volume: 237:29 Issue: 1 Pages: 1-7
  • DOI: 10.1007/s10751-016-1238-0
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Spin-Crossover Behavior of Hofmann-Type-Like Complex Fe(4,4'-bipyridine)Ni(CN)4.nH2O Depending on Guest Species (2016)
  • Author(s): Kazumasa Hosoya, Shin-ichi Nishikiori, Masashi Takahashi, Takafumi Kitazawa
  • Journal Title: Magnetochemistry Volume: 2,8 Issue: 1 Pages: 1-10
  • DOI: 10.3390/magnetochemistry2010008
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] ピラジン誘導体を配位子とするスピンクロスオーバー錯体 (2016)
  • Author(s): 北澤孝史、岸田貴範、関谷円香、高橋正
  • Journal Title: KURRI-EKR-6 (ISSN 2189-7107) Volume: 1 Pages: 16-19
  • Open Access
• [Presentation] Coordination Polymer Iron(II) Spin Crossover Compounds (2017)
  • Author(s): Takafumi Kitazawa
  • Organizer: The 3rd Annual World Congress of Smart Materials-2017
  • Place of Presentation: Bangkok(Thailand)
  • Year and Date: 2017-03-17
  • Int'l Joint Research / Invited
• [Presentation] Mossbauer Spectroscopic Characterization of Spin Crossover 2D Hofmann-like Coordination Polymer Materials (2017)
  • Author(s): Takafumi Kitazawa
  • Organizer: 3rd Mediterranean Conference on the Applications of the Mössbauer Effect
  • Int'l Joint Research / Invited
• [Presentation] 4-methylpyrimidineを用いた二次元Hofmann型構造を持つ二段階スピンクロスオーバー錯体 (2017)
  • Author(s): 北清航輔,岡林潤,北澤孝史
  • Organizer: 錯体化学会第67回討論会
• [Presentation] 4-methylpyrimidineを配位子とした多核錯体のスピンクロスオーバー挙動 (2017)
  • Author(s): 北清航輔,岡林潤,北澤孝史
  • Organizer: 日本化学会秋季事業第7回CSJ化学フェスタ2017
• [Presentation] ゲスト分子を包接した2次元ホフマン型錯体のスピンクロスオーバー挙動 (2017)
  • Author(s): 植木悠介,岡林潤, 北澤孝史
  • Organizer: 錯体化学会第67回討論会
• [Presentation] 分岐アルキル鎖を持つエチレングリコール系エーテルを含んだ新規シアン化カドミウム配位高分子の合成と結晶構造 (2017)
  • Author(s): 川﨑武志,北澤孝史
  • Organizer: 錯体化学会第67回討論会
• [Presentation] Ethyl Isonicotinate を配位子とするスピンクロスオーバー錯体 (2016)
  • Author(s): 北澤 孝史
  • Organizer: 平成28年度KUR専門研究会「短寿命RIを用いた核分光と核物性研究III」
  • Place of Presentation: 京都大学原子炉実験所(大阪府泉南郡）
  • Year and Date: 2016-12-20
• [Presentation] Crystal Structural Aspect of Thermal Spin State Switching in 2D Hofmann-like Coordination Polymer Frameworks (2016)
  • Author(s): Takafumi Kitazawa
  • Organizer: 14th Confernce of the Asian Crystallographic Association AsCA2016
  • Place of Presentation: Hanoi (Vietnam)
  • Year and Date: 2016-12-05
  • Int'l Joint Research
• [Presentation] Ethyl Isonicotinate を含む2D金属有機構造体のスピンクロスオーバー挙動 (2016)
  • Author(s): 椎名 瞳、岡林 潤、 高橋 正、 北澤 孝史「
  • Organizer: 第66回錯体化学討論会
  • Place of Presentation: 福岡大学(福岡県福岡市）
  • Year and Date: 2016-09-11
• [Presentation] エチレングリコールモノアルキルエーテルを含有するシアン化カドミウム系配位高分子の結晶構造 (2016)
  • Author(s): 川﨑 武志、 北澤 孝史
  • Organizer: 第66回錯体化学討論会
  • Place of Presentation: 福岡大学(福岡県福岡市）
  • Year and Date: 2016-09-11
• [Presentation] 芳香族ゲスト分子を包接した配位高分子錯体のスピンクロスオーバー制御 (2016)
  • Author(s): 植木 悠介、岡林 潤、 北澤 孝史
  • Organizer: 第66回錯体化学討論会
  • Place of Presentation: 福岡大学(福岡県福岡市）
  • Year and Date: 2016-09-10
• [Presentation] Spin Transition Depending on Guest Molecules into Hofmann-type Coordination Polymers (2016)
  • Author(s): Yusuke Ueki, Jun Okabayashi, Takafumi Kitazawa
  • Organizer: The 15th International Conference on Molecule-Based Magnets
  • Place of Presentation: 仙台国際センター(宮城県仙台市）
  • Year and Date: 2016-09-07
  • Int'l Joint Research
• [Presentation] Magnetic and Electronic Properties on Spin Crossover Complexes Fe(Ethyl Isonicotinate)2M(CN)4 (M = Ni, Pd, Pt) (2016)
  • Author(s): Hitomi Shiina, Jun Okabayashi, Masashi Takahashi, Takafumi Kitazawa
  • Organizer: The 15th International Conference on Molecule-Based Magnets
  • Place of Presentation: 仙台国際センター(宮城県仙台市）
  • Year and Date: 2016-09-07
  • Int'l Joint Research
• [Presentation] Spin Crossover Behavior in Hofmann-like Coordination Polymers Containing Various Pyridine Derivatives (2016)
  • Author(s): Takafumi Kitazawa
  • Organizer: 42nd International Conference on Coordination Chemistry
  • Place of Presentation: Brest (France)
  • Year and Date: 2016-07-07
  • Int'l Joint Research
• [Presentation] Guest insertion into Hofmann-type Coordination Polymer (2016)
  • Author(s): Yusuke Ueki, Jun Okabayashi, Takafumi Kitazawa
  • Organizer: 42nd International Conference on Coordination Chemistry
  • Place of Presentation: Brest(France)
  • Year and Date: 2016-07-04
  • Int'l Joint Research
• [Presentation] Aurophilic Interactions in Hofmann-type Coordination Polymers (2016)
  • Author(s): Takafumi Kitazawa, Yusuke Ueki, Itaru Tomori, Takashi Kosone
  • Organizer: CLUSPOM-1
  • Place of Presentation: Rennes(France)
  • Year and Date: 2016-06-30
  • Int'l Joint Research
• [Presentation] The 2016 EMN Meeting on Metal-Organic Frameworks (2016)
  • Author(s): Takafumi Kitazawa
  • Organizer: Structural Aspect of Spin Crossover Hofamnn-like Metal-Organic Frameworks
  • Place of Presentation: Qingdao(China)
  • Year and Date: 2016-06-14
  • Int'l Joint Research / Invited
• [Presentation] 2D Hofmann-like Coordination Polymers with Spin Crossover Behaviors (2016)
  • Author(s): Takafumi Kitazawa
  • Organizer: The EMN 2D Materials Meeting 2016
  • Place of Presentation: San Sebastioan(Spain)
  • Year and Date: 2016-05-22
  • Int'l Joint Research / Invited
• [Presentation] Spin Crossover Coordination Polymer Compounds with Hofmann-like Frameworks (2016)
  • Author(s): Takafumi Kitazawa
  • Organizer: EMN Meeting on Polymer 2016
  • Place of Presentation: Hong Kong (China)
  • Year and Date: 2016-01-13
  • Int'l Joint Research / Invited
• [Presentation] Hofmann-like spin crossover coordination polymer with 4-Xpyridine ligands (2015)
  • Author(s): Takafumi Kitazawa
  • Organizer: Pacifichem 2015
  • Place of Presentation: Hawai (USA)
  • Year and Date: 2015-12-18
  • Int'l Joint Research
• [Presentation] ピラジン誘導体を配位子とするスピンクロスオーバー錯体 (2015)
  • Author(s): 北澤孝史
  • Organizer: 平成27年度KUR専門研究会「短寿命RIを用いた核分光と核物性研究」
  • Place of Presentation: 京都大学原子炉実験所（大阪府泉南郡）
  • Year and Date: 2015-11-04
• [Presentation] イソニコチン酸エチルを配位子とする２次元スピンクロスオーバー錯体 (2015)
  • Author(s): 椎名瞳、岡林潤、北澤孝史
  • Organizer: 錯体化学会第65回討論会
  • Place of Presentation: 奈良女子大学 (奈良県奈良市）
  • Year and Date: 2015-09-22
• [Presentation] 2-Methylpyrazineによる２次元配位高分子錯体のスピンクロスオーバー制御 (2015)
  • Author(s): 関谷円香、岸田貴範、岡林潤、北澤孝史
  • Organizer: 錯体化学会第65回討論会
  • Place of Presentation: 奈良女子大学 (奈良県奈良市）
  • Year and Date: 2015-09-22
• [Presentation] Co2+によるホフマン型スピンクロスオーバー錯体の金属希釈効果 (2015)
  • Author(s): 松本晋也、岡林潤、北澤孝史
  • Organizer: 錯体化学会第65回討論会
  • Place of Presentation: 奈良女子大学 (奈良県奈良市）
  • Year and Date: 2015-09-22
• [Presentation] Mossbauer spectroscopic study on spin crossover coordination polymer Fe(3-Clpy)2[Pd(CN)4] (2015)
  • Author(s): Takafumi Kitazawa, Madoka Sekiya, Masashi Takahashi
  • Organizer: The 33nd International Conference on the Application on the Mossbauer Effect
  • Place of Presentation: Hamburg(Germany)
  • Year and Date: 2015-09-16
  • Int'l Joint Research