Studies on Crystal Structures and Photophysical propertiea of Luminescent Multi-nuclear d10-metal Complexes

• Project/Area Number: 21550065
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Inorganic chemistry
• Research Institution: University of Hyogo
• Principal Investigator: OZAWA Yoshiki 兵庫県立大学, 大学院・物質理学研究科, 准教授 (40204200)
• Project Period (FY): 2009 – 2011
• Project Status: Completed (Fiscal Year 2011)
• Budget Amount: ¥5,070,000 (Direct Cost: ¥3,900,000、Indirect Cost: ¥1,170,000); Fiscal Year 2011: ¥650,000 (Direct Cost: ¥500,000、Indirect Cost: ¥150,000); Fiscal Year 2010: ¥780,000 (Direct Cost: ¥600,000、Indirect Cost: ¥180,000); Fiscal Year 2009: ¥3,640,000 (Direct Cost: ¥2,800,000、Indirect Cost: ¥840,000)
• Keywords: 銅錯体 / 銀錯体 / 多核金属錯体 / フォトルミネッセンス / 光励起構造 / 量子計算 / サーモクロミズム / 光励起構造解析 / 単結晶X線構造解析 / 金錯体 / メカノクロミズム / 高圧粉末結晶構造解析 / 放射光 / トリフェニルホスフィン

Research Abstract

Syntheses and photophysical properties of halogen-or sulferbridged multinuclear metal complexes have been studied. Photoluminescence thermochromism is found for the tetranucler copper(I) iodide triphenylphosphine complex. The single crystal emits green-yellow color under UV illumination at 300 K, which turns orange at 78 K. Multi-temperature X-ray structure analyses demonstrate that the photoemission energy shifts are correlated with a deformation of four-metal core. This phenomenon suggests that the emission properties of these complexes can respond to outer environments in the crystalline-or solid-states.

Research Products

• [Journal Article] Preparation, crystal structures, spectroscopic and thermal analyses of two co-crystals of[M(H_2O)_6][M(dipic)_2] and(atrH)_2[M(dipic)_2](M=Zn, Ni, dipic=dipicolinate ; atr ;=3-amino-1H-1, 2, 4-triazole) with isostructural crystal systems (2012)
  • Author(s): Tabatabaee, M.; Tahriri, M.; Tahriri, M.; Ozawa, Y.; Neumuller, B.; Fujioka, H.; Toriumi, K.
  • Journal Title: Polyhedron Volume: 33 Issue: 1 Pages: 336-340
  • DOI: 10.1016/j.poly.2011.11.056
  • Peer Reviewed
• [Journal Article] [H_xTeV_9O_28]^<(5-x)->(x=1 and 2): Vanadotellurates with Decavanadate Structure (2011)
  • Author(s): Konaka, S.; Ozawa, Y.; Shonaka, T.; Watanabe, S.; Yagasaki, A.
  • Journal Title: Inorg. Chem Volume: 50 Issue: 13 Pages: 6183-6188
  • DOI: 10.1021/ic200438p
  • Peer Reviewed
• [Journal Article] Which Is The Most Basic Oxygen in [Ta_6O_<19>]^<8->?--Synthesis and Structural Characterization of [H_2Ta_6O_<19>]^<6-> (2011)
  • Author(s): Matsumoto, Miki; Ozawa, Yoshiki; Yagasaki, Atsushi
  • Journal Title: Inorganic Chemistry Communications Volume: 14 Issue: 1 Pages: 115-117
  • DOI: 10.1016/j.inoche.2010.09.045
  • Peer Reviewed
• [Journal Article] Flexibility of cubane-like Cu_4I_4 framework : temperature dependence of molecular structure and luminescence thermochromism of[Cu_4I_4(PPh_3)_4] in two polymorphic crystalline states (2010)
  • Author(s): Kitagawa, H.; Ozawa, Y.; Toriumi, K.
  • Journal Title: Chem. Commun Volume: 46 Issue: 34 Pages: 6302-6304
  • DOI: 10.1039/c0cc01434f
  • Peer Reviewed
• [Journal Article] Reversible dimerization of decaniobate (2010)
  • Author(s): Matsumoto, M.; Ozawa, Y.; Yagasaki, A.
  • Journal Title: Polyhedron Volume: 29 Issue: 10 Pages: 2196-2201
  • DOI: 10.1016/j.poly.2010.04.016
  • Peer Reviewed
• [Journal Article] Polymorphic crystal approach to changing the emission of [AuCl(PPh ₃)₂], analyzed by direct observation of the photoexcited structures by X-ray photocrystallography (2010)
  • Author(s): Hoshino, M.; Uekusa, H.; Ishii, S.; Otsuka, T.; Kaizu, Y.; Ozawa, Y.; Toriumi, K.
  • Journal Title: Inorg. Chem Volume: 49 Issue: 16 Pages: 7257
  • DOI: 10.1021/ic901261u
  • Peer Reviewed
• [Journal Article] Flexibility of cubane-like Cu_4I_4 framework : temperature dependence of molecular structure and luminescence thermochromism of [Cu_4I_4(PPh_3)_4] in two polymorphic crystalline states (2010)
  • Author(s): Kitagawa, Hakuba ; Ozawa, Yoshiki, Toriumi, Koshiro
  • Journal Title: Chemical Communications Volume: 46 Pages: 6302-6304
  • Peer Reviewed
• [Journal Article] Structure and Electronic Configuration of an Iron(II) Complex in a LIESST State : A Pump and Probe Method (2009)
  • Author(s): Sheu, C.-F.; Chen, K.; Chen, S.-M.; Wen, Y.-S.; Lee, G.-H.; Chen, J.-M.; Lee, J.-F.; Cheng, B.-M.; Sheu, H.-S.; Yasuda, N.; Ozawa, Y.; Toriumi, K.; Wang, Y.
  • Journal Title: Chem. Eur. J. Volume: 15(10) Issue: 10 Pages: 2384-2393
  • DOI: 10.1002/chem.200802279
  • Peer Reviewed
• [Journal Article] Structure an Electronic Configuration of an Iron(II)Complex in a LIESST State : A Pump and Probe Method (2009)
  • Author(s): Sheu, C.-F., Chen, K., Chen, S.-M., Wen, Y.-S., Lee, G.-H., Chen, J.-M., Lee, J.-F., Cheng, B.-M., Sheu, H.-S., Yasuda, N., Ozawa, Y., Toriumi, K., Wang, Y.
  • Journal Title: Chemistry-A European Journal 15 Pages: 2384-2393
  • Peer Reviewed
• [Presentation] 3-ピコリンを配位子とするキュバン型ヨウ化銅(I)四核錯体の多形結晶の構造と発光特性の温度依存性 (2012)
  • Author(s): 山崎祥太, 小澤芳樹, 鳥海幸四郎
  • Organizer: 日本化学会第92春季年会
  • Place of Presentation: 慶應大学
  • Year and Date: 2012-03-26
• [Presentation] 3-ピコリンを配位子とするキュバン型ヨウ化銅(I)四核錯体の多形結晶の構造と発光特性の温度依存性 (2012)
  • Author(s): 山崎祥太, 小澤芳樹, 鳥海幸四郎
  • Organizer: 日本化学会第92春季年会
  • Place of Presentation: 慶応大学(神奈川県)
  • Year and Date: 2012-03-26
• [Presentation] 2-キノリンチオールを配位子とする六核銀(I)および銅(I)錯体の構造と発光挙動 (2012)
  • Author(s): 増永あずさ, 小澤芳樹, 安田伸広, 鳥海幸四郎
  • Organizer: 日本化学会第92春季年会
  • Place of Presentation: 慶應大学
  • Year and Date: 2012-03-25
• [Presentation] 2-キノリンチオールを配位子とする六核銀(I)および銅(I)錯体の構造と発光挙動 (2012)
  • Author(s): 増永あずさ, 小澤芳樹, 安田伸広, 鳥海幸四郎
  • Organizer: 日本化学会第92春季年会
  • Place of Presentation: 慶応大学(神奈川県)
  • Year and Date: 2012-03-25
• [Presentation] 発光性銅(I)ピリジンチオラト多核錯体の極微小単結晶構造解析 (2011)
  • Author(s): 小澤芳樹, 今川理恵, 安田伸広, 鳥海幸四郎
  • Organizer: 日本結晶学会2011年会
  • Place of Presentation: 北海道大学学術交流会館
  • Year and Date: 2011-11-24
• [Presentation] 発光性金(I)-銅(I)および金(I)-銀(I)六核混合金属錯体の合成と構造 (2011)
  • Author(s): 藤岡裕子, 小澤芳樹, 安田伸広, 鳥海幸四郎
  • Organizer: 錯体化学会第61回討論会
  • Place of Presentation: 岡山理科大学
  • Year and Date: 2011-09-18
• [Presentation] 発光性金(I)-銅(I)および金(I)-銀(I)六核混合金属錯体の合成と構造 (2011)
  • Author(s): 藤岡裕子, 小澤芳樹, 安田伸広, 鳥海幸四郎
  • Organizer: 錯体化学会第61回討論会
  • Place of Presentation: 岡山理科大学(岡山県)
  • Year and Date: 2011-09-18
• [Presentation] 発光性ハロゲン化銅(I)ポリマー錯体[Cu2I2(PPh3) 2(pz)]_∞の多形結晶とメカノクロミズム (2011)
  • Author(s): 山本和矢, 小澤芳樹, 鳥海幸四郎
  • Organizer: 錯体化学会第61回討論会
  • Place of Presentation: 岡山理科大学
  • Year and Date: 2011-09-17
• [Presentation] 発光性ハロゲン化銅(I)ポリマー錯体[Cu_2I_2(PPh_3)_2(pz)]_∞の多形結晶とメカノクロミズム (2011)
  • Author(s): 山本和矢, 小澤芳樹, 鳥海幸四郎
  • Organizer: 錯体化学会第61回討論会
  • Place of Presentation: 岡山理科大学(岡山県)
  • Year and Date: 2011-09-17
• [Presentation] Photoexcited state crystallography of luminescent hexanuclear d^<10> metal complexes (2011)
  • Author(s): Ozawa Yoshiki, Ishida Toru, Toriumi Koshiro
  • Organizer: XXI Congress and General Assembly of the International Union of Crystallography
  • Place of Presentation: Palacio Municipal de Congresos, Madrid, Spain
  • Year and Date: 2011-08-28
• [Presentation] Photoexcited state crystallography of luminescent hexanuclear d^<10> metal complexes (2011)
  • Author(s): Ozawa, Yoshiki; Ishida, Toru; Toriumi, Koshiro
  • Organizer: XXI IUCr Congress
  • Place of Presentation: Madrid (Spain)
  • Year and Date: 2011-08-28
• [Presentation] 結晶中で柔軟に変形する発光性d^<10>金属多核錯体の構造と物性 (2011)
  • Author(s): 小澤芳樹, 北川白馬, 今川理恵, 上田紘平, 鳥海幸四郎
  • Organizer: 日本化学会第91春季年会
  • Place of Presentation: 神奈川大学横浜キャンパス
  • Year and Date: 2011-03-27
• [Presentation] Direct observation of photo-excited state geometrical change of copper(I) hexanuclear complex by crystallographic studies under photo-illumination (2010)
  • Author(s): Ozawa, Yoshiki ; Ishida, Toru ; Toriumi, Koshiro
  • Organizer: The 2010 International Chemical Congress of Pacific Basin Societies
  • Place of Presentation: Honolulu, Hawaii, U. S.
  • Year and Date: 2010-12-18
• [Presentation] Flexible cubane-like framework in crystalline state : structure and luminescent properties of[Cu_4I_4(PPh_3)_4] (2010)
  • Author(s): Kitagawa Hakuba, Ozawa Yoshiki, Akahama Yuichi, Kawamura Haruki, Toriumi Koshiro
  • Organizer: The 2010 International Chemical Congress of Pacific Basin Societies
  • Place of Presentation: Honolulu, Hawaii, U. S.
  • Year and Date: 2010-12-18
• [Presentation] Direct observation of photo-excited state geometrical change of copper(I) hexanuclear complex by crystallographic studies under photo-illumination. (2010)
  • Author(s): Ozawa, Yoshiki ; Ishida, Toru ; Toriumi, Koshiro
  • Organizer: The 2010 International Chemical Congress of Pacific Basin Societies
  • Place of Presentation: Honolulu, Hawaii, US
  • Year and Date: 2010-12-18
• [Presentation] 結晶中で柔軟に変形する銀(I)六核錯体の構造と発光挙動 (2010)
  • Author(s): 上田紘平, 小澤芳樹, 鳥海幸四郎
  • Organizer: 日本結晶学会2010年会
  • Place of Presentation: 大阪大学
  • Year and Date: 2010-12-04
• [Presentation] 銀(I)銅(I)混合金属六核錯体の合成,結晶構造および発光特性 (2010)
  • Author(s): 今川理恵, 小澤芳樹, 鳥海幸四郎
  • Organizer: 日本結晶学会2010年会
  • Place of Presentation: 大阪大学
  • Year and Date: 2010-12-03
• [Presentation] Single crystal structure analyses of photo-excited states of photoluminescent hexanuclear d10 metal complexes (2010)
  • Author(s): Ozawa Yoshiki, Ishida Toru, Kimura Kimihiro, Toriumi Koshiro
  • Organizer: Conference of the Asian Crystallographic Association
  • Place of Presentation: BEXCO, Busan, South Korea
  • Year and Date: 2010-11-01
• [Presentation] Syntheses, structures and photoluminescence properties of hexanuclear gold(I)-silver(I) mixed metal complexes (2010)
  • Author(s): Fujioka Hiroko, Ozawa Yoshiki, Toriumi Koshiro
  • Organizer: Conference of the Asian Crystallographic Association
  • Place of Presentation: BEXCO, Busan, South Korea
  • Year and Date: 2010-11-01
• [Presentation] Structural change and luminescent properties of[Cu_4I_4(PPh-3)_4] under high pressure (2010)
  • Author(s): Kitagawa Hakuba, Ozawa Yoshiki, Akahama Yuichi, Kawamura Haruki, Toriumi Koshiro
  • Organizer: 第60回錯体化学討論会
  • Place of Presentation: Osaka
  • Year and Date: 2010-09-27
• [Presentation] メカノクロミズムを示す発光性ハロゲン化銀(I)ポリマー錯体 (2010)
  • Author(s): 山本和矢, 小澤芳樹, 鳥海幸四郎
  • Organizer: 第60回錯体化学討論会
  • Place of Presentation: Osaka
  • Year and Date: 2010-09-27
• [Presentation] 銀(I)銅(I)混合金属六核錯体の合成,構造および発光特性 (2010)
  • Author(s): 今川理恵, 小澤芳樹, 鳥海幸四郎
  • Organizer: 日本化学会第90春季年会
  • Place of Presentation: 近畿大学
  • Year and Date: 2010-03-28
• [Presentation] エチルピリジンチオラト銀(I)金(I)混合金属錯体[Ag_4Au_2(epyt)_4Cl_2]の合成と結晶構造 (2009)
  • Author(s): 藤岡裕子, 小澤芳樹, 鳥海幸四郎
  • Organizer: 日本結晶学会2009年会
  • Place of Presentation: 関西学院大学
  • Year and Date: 2009-12-05
• [Presentation] 結晶中で柔軟に変形するキュバン型銅(I)錯体[Cu_4I_4(PPh_3)_4]の構造と発光挙動 (2009)
  • Author(s): 北川白馬, 小澤芳樹, 川村春樹, 赤浜裕一, 鳥海幸四郎
  • Organizer: 日本結晶学会2009年会
  • Place of Presentation: 関西学院大学
  • Year and Date: 2009-12-05
• [Presentation] キュバン型銅(I)錯体[Cu_4I_4(PPh_3)_4]の多形結晶の高圧下での発光特性 (2009)
  • Author(s): 北川白馬, 小澤芳樹, 川村春樹, 鳥海幸四郎
  • Organizer: 第59回錯体化学討論会
  • Place of Presentation: 長崎大学
  • Year and Date: 2009-09-25
• [Presentation] 結晶中で柔軟に変形するキュバン型銅(I)錯体[Cu_4I_4(PPh_3)_4]の構造と発光挙動 (2009)
  • Author(s): 北川白馬, 小澤芳樹, 川村春樹, 赤浜裕一, 鳥海幸四郎
  • Organizer: 日本結晶学会2009年会
  • Place of Presentation: 関西学院大学, 西宮キャンパス
• [Remarks]
  • URL: http://www.sci.u-hyogo.ac.jp/material/cryst_struct/index-j.html
• [Remarks]
  • URL: http://www.sci.u-hyogo.ac.jp/material/cryst_struct/index-j.html
• [Remarks]
  • URL: http://www.sci.u-hyogo.ac.jp/material/cryst_struct/index-j.html