Electron density study of photo-functional molecular crystals by complementary use of neutron and X-ray diffraction techniques

• Project/Area Number: 16K05028
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Research Field: Quantum beam science
• Research Institution: Japan Atomic Energy Agency
• Principal Investigator: Ohhara Takashi 国立研究開発法人日本原子力研究開発機構, 原子力科学研究部門 J－PARCセンター, 研究主幹 (60391249)
• Project Period (FY): 2016-04-01 – 2020-03-31
• Project Status: Completed (Fiscal Year 2019)
• Budget Amount: ¥4,680,000 (Direct Cost: ¥3,600,000、Indirect Cost: ¥1,080,000); Fiscal Year 2018: ¥910,000 (Direct Cost: ¥700,000、Indirect Cost: ¥210,000); Fiscal Year 2017: ¥2,340,000 (Direct Cost: ¥1,800,000、Indirect Cost: ¥540,000); Fiscal Year 2016: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
• Keywords: 量子ビーム測定手法 / 有機光機能性結晶 / J-PARC / 単結晶中性子回折 / X-N解析法 / 価電子密度解析 / 量子ビーム科学 / 構造・機能材料 / 量子ビーム / Ｊ－ＰＡＲC

Outline of Final Research Achievements

This work achieved the visualization of electron density in a molecular crystal by the "X-N analysis" using a laboratory X-ray diffractometer and a time-of-flight single crystal neutron diffractometer SENJU at J-PARC. In addition, two polymorphs of a photo-functional molecular crystal, 2-(2'-hydroxyphenyl)benzimidazole, were analysed by X-ray and neutron diffraction, quantum calculation and spectroscopic analyses. The results showed that a cooperative act of an inter-molecular and an intra-molecular hydrogen bonding in the crystal leads the differences of the fluorescence behavior between polymorphs.

Academic Significance and Societal Importance of the Research Achievements

本研究では補正用データの測定法を改良することで、TOF単結晶中性子回折計であるSENJUで得られる回折データが有機結晶のX-N構造解析に十分使えることを実証することができた。これは、実際の機能性有機結晶の研究に対し、原子核の観察だけでなく電子密度の観察という価値を単結晶中性子回折法に付加したものである。また、一連の光機能性結晶の研究は、今後光機能性を高めた誘導体結晶をを開発するうえで重要な知見と言える。

Research Products

• [Journal Article] Crystal Structure and Cation Distribution of the X-type Hexaferrite Sr2Co2Fe28O46 (2020)
  • Author(s): M. Komabuchi, D. Urushihara, T. Asaka, K. Fukuda, T. Ohhara, K. Munakata and Y. Ishikawa
  • Journal Title: J. Phys. Soc. Jpn. Volume: 89 Issue: 3 Pages: 034601-034601
  • DOI: 10.7566/jpsj.89.034601
  • NAID: 40022185692
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Multi-Step Magnetic Transitions in EuNiIn4 (2020)
  • Author(s): S. Ikeda, K. kneko, Y. Tanaka, T. Kawasaki, T. Hanashima, K. Munakata, A. Nakao, R. Kiyanagi, T. Ohhara, K. Mochizuki, A. Kondo, K. Kindo, Y. Homma, M. D. Frontzek, H. Kobayashi
  • Journal Title: J. Phys. Soc. Jpn. Volume: 89 Issue: 1 Pages: 014707-014707
  • DOI: 10.7566/jpsj.89.014707
  • NAID: 210000157872
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] muSR and Neutron Scattering Studied on Possible Partially-Disordered Magnetic State Coexisting with Heavy Quasiparticles in SmPt2Si2 (2020)
  • Author(s): Naoki Nakamura, Ryuji Higashinaka, Kengo Fushiya, Ryo Tsubota, Takashi U. Ito, Wataru Higemoto, Akiko Nakao, Ryoji Kiyanagi, Takashi Ohhara, Koji Kaneko, Tatsuma D. Matsuda, and Yuji Aoki
  • Journal Title: J. Phys. Soc. Cof. Volume: 29 Pages: 12009-12009
  • DOI: 10.7566/jpscp.29.012009
  • Peer Reviewed / Open Access
• [Journal Article] Successive Phase Transitions in R3Ir4Sn13 (R: La and Ce) Investigated Using Neutron and X-ray Diffraction (2020)
  • Author(s): Nakazato Seiya、Iwasa Kazuaki、Hashimoto Daisuke、Shiozawa Mami、Kuwahara Keitaro、Nakao Hironori、Sagayama Hajime、Ishikado Motoyuki、Ohhara Takashi、Nakao Akiko、Munakata Koji、Kiyanagi Ryoji
  • Journal Title: JPS Conf. Proc. Volume: 30 Pages: 011128-011128
  • DOI: 10.7566/jpscp.30.011128
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Recent Researches of Physical Properties and Reactions in Molecular Crystals Using Neutron Diffraction Technique (2019)
  • Author(s): OHHARA Takashi
  • Journal Title: Nihon Kessho Gakkaishi Volume: 61 Issue: 3 Pages: 153-154
  • DOI: 10.5940/jcrsj.61.153
  • NAID: 130007698394
  • ISSN: 0369-4585, 1884-5576
  • Year and Date: 2019-08-31
  • Peer Reviewed / Open Access
• [Journal Article] Magnetic, thermal, and neutron diffraction studies of a coordination polymer: bis(glycolato)cobalt(ii) (2019)
  • Author(s): Nakane Tomohiro、Yoneyama Shota、Kodama Takeshi、Kikuchi Koichi、Nakao Akiko、Ohhara Takashi、Higashinaka Ryuji、Matsuda Tatsuma D.、Aoki Yuji、Fujita Wataru
  • Journal Title: Dalton Transactions Volume: 48 Issue: 1 Pages: 333-338
  • DOI: 10.1039/c8dt04358b
  • Peer Reviewed / Open Access
• [Journal Article] Unique Helical Magnetic Order and Field-Induced Phase in Trillium Lattice Antiferromagnet EuPtSi (2019)
  • Author(s): Kaneko Koji、Frontzek Matthias D.、Matsuda Masaaki、Nakao Akiko、Munakata Koji、Ohhara Takashi、Kakihana Masashi、Haga Yoshinori、Hedo Masato、Nakama Takao、Onuki Yoshichika
  • Journal Title: Journal of the Physical Society of Japan Volume: 88 Issue: 1 Pages: 013702-013702
  • DOI: 10.7566/jpsj.88.013702
  • NAID: 40021772136
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] High oxide-ion conductivity by the overbonded channel oxygens in Si-deficient La9.565(Si5.826□0.174)O26 apatite without interstitial oxygens (2018)
  • Author(s): Kotaro Fujii, Masatomo Yashima, Keisuke Hibino, Masahiro Shiraiwa, Koichiro Fukuda, Susumu Nakayama, Nobuo Ishizawa, Takayasu Hanashima, Takashi Ohhara
  • Journal Title: J. Mater. Chem. A Volume: 印刷中 Issue: 23 Pages: 10835-10846
  • DOI: 10.1039/c8ta02237b
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Structure Analysis and Derivation of Deformed Electron Density Distribution of Polydiacetylene Giant Single Crystal by the Combination of X-ray and Neutron Diffraction Data (2018)
  • Author(s): Tashiro Kohji、Kusaka Katsuhiro、Hosoya Takaaki、Ohhara Takashi、Hanesaka Makoto、Yoshizawa Yoshinori、Yamamoto Hiroko、Niimura Nobuo、Tanaka Ichiro、Kurihara Kazuo、Kuroki Ryota、Tamada Taro
  • Journal Title: Macromolecules Volume: 51 Issue: 11 Pages: 3911-3922
  • DOI: 10.1021/acs.macromol.8b00650
  • Peer Reviewed
• [Journal Article] Status of the neutron time-of-flight single-crystal diffraction data-processing software STARGazer (2018)
  • Author(s): Yano Naomine、Yamada Taro、Hosoya Takaaki、Ohhara Takashi、Tanaka Ichiro、Niimura Nobuo、Kusaka Katsuhiro
  • Journal Title: Acta Crystallographica Section D Structural Biology Volume: 74 Issue: 11 Pages: 1041-1052
  • DOI: 10.1107/s2059798318012081
  • Peer Reviewed / Open Access
• [Journal Article] Magnetic-Ordering Propagation Vectors of Terbium Hexaboride Revisited (2018)
  • Author(s): Iwasa Kazuaki、Iga Fumitoshi、Moyoshi Taketo、Nakao Akiko、Ohhara Takashi
  • Journal Title: Journal of the Physical Society of Japan Volume: 87 Issue: 6 Pages: 064705-064705
  • DOI: 10.7566/jpsj.87.064705
  • NAID: 210000134869
  • Peer Reviewed / Open Access
• [Journal Article] Mn2VAl Heusler alloy thin films: appearance of antiferromagnetism and exchange bias in a layered structure with Fe (2018)
  • Author(s): Tsuchiya Tomoki、Kobayashi Ryota、Kubota Takahide、Saito Kotaro、Ono Kanta、Ohhara Takashi、Nakao Akiko、Takanashi Koki
  • Journal Title: Journal of Physics D: Applied Physics Volume: 51 Issue: 6 Pages: 065001-065001
  • DOI: 10.1088/1361-6463/aaa41a
  • Peer Reviewed / Open Access
• [Journal Article] Neutron-scattering study of yttrium iron garnet (2018)
  • Author(s): S. Shamoto, T. U. Ito, H. Onishi, H. Yamauchi, Y. Inamura, M. Matsuura, M. Akatsu, K. Kodama, A. Nakao, T. Moyoshi, K. Munakata,T. Ohhara, M. Nakamura, S. Ohira-Kawamura, Y. Nemoto, and K. Shibata
  • Journal Title: Physical Review B Volume: 97 Issue: 5 Pages: 1-9
  • DOI: 10.1103/physrevb.97.054429
  • Peer Reviewed / Open Access
• [Journal Article] Non-aqueous selective synthesis of orthosilicic acid and its oligomers (2017)
  • Author(s): Igarashi Masayasu、Matsumoto Tomohiro、Yagihashi Fujio、Yamashita Hiroshi、Ohhara Takashi、Hanashima Takayasu、Nakao Akiko、Moyoshi Taketo、Sato Kazuhiko、Shimada Shigeru
  • Journal Title: Nature Communications Volume: 8 Issue: 1
  • DOI: 10.1038/s41467-017-00168-5
  • Peer Reviewed / Open Access
• [Journal Article] Quantum twin spectra in nanocrystalline silicon (2017)
  • Author(s): Matsumoto Takahiro、Ohhara Takashi、Sugimoto Hidehiko、Bennington Stephen M.、Ikeda Susumu
  • Journal Title: Physical Review Materials Volume: 1 Issue: 5
  • DOI: 10.1103/physrevmaterials.1.051601
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Encapsulating Mobile Proton Carriers into Structural Defects in Coordination Polymer Crystals: High Anhydrous Proton Conduction and Fuel Cell Application (2016)
  • Author(s): Munehiro Inukai, Satoshi Horike, Tomoya Itakura, Ryota Shinozaki, Naoki Ogiwara, Daiki Umeyama, Sanjog Nagarkar, Yusuke Nishiyama, Michal Malon, Akari Hayashi, Takashi Ohhara, Ryoji Kiyanagi, Susumu Kitagawa
  • Journal Title: J. Am. Chem. Soc. Volume: 138 Issue: 27 Pages: 8505-8511
  • DOI: 10.1021/jacs.6b03625
  • Peer Reviewed
• [Journal Article] Molecular Gyrotops with a Five-Membered Heteroaromatic Ring: Synthesis, Temperature-Dependent Orientation of Dipolar Rotors inside the Crystal, and its Birefringence Change (2016)
  • Author(s): T. Masuda, J. Arase, Y. Inagaki, M. Kawahata, K. Yamaguchi, T. Ohhara, A. Nakao, H. Momma, E. Kwon, W. Setaka
  • Journal Title: Cryst. Growth Des. Volume: 16 Issue: 8 Pages: 4392-4401
  • DOI: 10.1021/acs.cgd.6b00508
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Magnetic structure of divalent europium compound EuGa4 studied by single crystal time-of-flight neutron diffraction (2016)
  • Author(s): T. Kawasaki, K. Kaneko, A. Nakamura, N. Aso, M. Hedo, T. Nakama, T. Ohhara, R. Kiyanagi, K. Oikawa, I. Tamura, A. Nakao, K. Munakata, T. Hanashima and Y. Onuki
  • Journal Title: J. Phys. Soc. Jpn. Volume: 85 Issue: 11 Pages: 114711-114715
  • DOI: 10.7566/jpsj.85.114711
  • NAID: 210000134159
  • Peer Reviewed / Open Access
• [Presentation] 結晶構造解析におけるMLFと3号炉の相補的利用を考える (2020)
  • Author(s): 大原高志
  • Organizer: 量子ビームサイエンスフェスタ2019
  • Invited
• [Presentation] The latest status of a TOF single crystal neutron diffractometer SENJU at J-PARC (2019)
  • Author(s): Takashi Ohhara, Ryoji Kiyanagi, Akiko Nakao, Koji Munakata, Yoshihisa Ishikawa, Kentaro Moriyama, Itaru Tamura and Koji Kaneko
  • Organizer: The 3rd J-PARC Symposium (J-PARC2019)
  • Int'l Joint Research
• [Presentation] The latest status of a TOF single crystal neutron diffractometer SENJU at J-PARC (2019)
  • Author(s): Takashi Ohhara, Ryoji Kiyanagi, Akiko Nakao, Koji Munakata, Yoshihisa Ishikawa, Kentaro Moriyama, Itaru Tamura and Koji Kaneko
  • Organizer: 16th Conference of the Asian Crystallographic Association
  • Int'l Joint Research
• [Presentation] MLFの単結晶回折計SENJUによる中性子構造解析 (2019)
  • Author(s): 大原高志
  • Organizer: 日本セラミックス協会2019年年会サテライトプログラム 第1回新材料の開発を目指した構造科学研究会
  • Invited
• [Presentation] Temperature-induced intramolecular proton transfer in a novel polymorph of 2-(2'-hydroxyphenyl)benzimidazole crystal (2018)
  • Author(s): Takashi Ohhara
  • Organizer: Asian Crystallographic Association Conference 2018
  • Int'l Joint Research / Invited
• [Presentation] Latest status of a TOF single crystal neutron diffractometer SENJU at J-PARC (2017)
  • Author(s): Takashi Ohhara
  • Organizer: 1st European Neutron Diffraction Single-Crystal Workshop
  • Int'l Joint Research / Invited
• [Presentation] Single Crystal Neutron Diffraction Study of a Crystalline-State Photoisomerization in a 3-Cyanopropyl Cobaloxime Complex (2017)
  • Author(s): Takashi Ohhara, Ryoji Kiyanagi, Kenichi Oikawa, Takuro Kawasaki, Koji Kaneko, Itaru Tamura, Akiko Nakao, Takayasu Hanashima, Koji Munakata
  • Organizer: International Conference on Neutron Scattering 2017
  • Int'l Joint Research
• [Presentation] Temperature-dependence of the crystal structure of 2-(2’-hydroxyphenyl)benzimidazole studied by single-crystal neutron diffraction (2017)
  • Author(s): Takashi Ohhara, Ryoji Kiyanagi, Akiko Nakao, Koji Munakata, Taketo Moyoshi, Takayasu Hanashima and Takaaki Hosoya
  • Organizer: 24th Congress and General Assembly of the International Union of Crystallography
  • Int'l Joint Research
• [Presentation] Deuteration in Crystal Chemistry (2017)
  • Author(s): Takashi Ohhara
  • Organizer: International Workshop: Deuterated Materials Enhancing Neutron Science for Structure Function Applications
  • Int'l Joint Research / Invited
• [Presentation] TOF単結晶中性子回折計SENJUの最新状況 (2016)
  • Author(s): 大原高志、鬼柳亮嗣、中尾朗子、宗像孝司、茂吉武人、森山健太郎
  • Organizer: 日本中性子科学会第16回年会
  • Place of Presentation: 名古屋大学(愛知県名古屋市)
  • Year and Date: 2016-12-04
• [Presentation] Recent advances of a single crystal neutron diffractometer SENJU at J-PARC (2016)
  • Author(s): T. Ohhara, R. Kiyanagi, A. Nakao, K. Munakata, T. Moyoshi, K. Moriyama, T. Hanashima, T. Kuroda
  • Organizer: 14th Conference of the Asian Crystallographic Association
  • Place of Presentation: ハノイ工科大学(Hanoi, Vietnam)
  • Year and Date: 2016-12-04
  • Int'l Joint Research / Invited
• [Presentation] Neutron structure analysis at J-PARC (2016)
  • Author(s): Takashi Ohhara
  • 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
  • Invited
• [Presentation] Single crystal neutron diffraction experiment at J-PARC (2016)
  • Author(s): Takashi Ohhara
  • Organizer: Workshop on Advanced Structural Study
  • Place of Presentation: 筑波大学(茨城県つくば市)
  • Int'l Joint Research / Invited
• [Remarks] J-PARC MLF BL18 SENJU
  • URL: https://www.youtube.com/watch?v=yIUHqm2bl1M
• [Remarks] 200年にわたる謎に終止符、ガラスの基本単位の構造を決定
  • URL: http://www.j-parc.jp/ja/topics/2017/Press170727.html