Creation of New pi-Electron Systems with Novel Properties and Functions

1993 Fiscal Year Final Research Report Summary

• Project/Area Number: 04453027
• Research Category: Grant-in-Aid for General Scientific Research (B)
• Allocation Type: Single-year Grants
• Research Field: 有機化学一般
• Research Institution: Tokyo Metropolitan University
• Principal Investigator: IYODA Masahiko Faculty of Science, Tokyo Metropolitan University, Professor, 理学部, 教授 (50115995)
• Co-Investigator(Kenkyū-buntansha): SASAKI Shigeru Faculty of Science, Tokyo Metropolitan University, Research Assistant, 理学部, 助手 (90254143) ; YOSHIDA Masato Faculty of Science, Tokyo Metropolitan University, Research Assistant, 理学部, 助手 (50137030) ; MATSUYAMA Haruo Faculty of Science, Tokyo Metropolitan University, Assistant Professor, 理学部, 助教授 (30087118)
• Project Period (FY): 1992 – 1993
• Keywords: conductivity / Ferromagnetic interaction / donor / tetrathiafulvalene / ferrocene / palladium catalyzed reaction / cross-coupling / radical salt

Research Abstract

In order to create the compounds which have both conductivity and ferromagnetic properties, we designed the donor systems bearing TTF- or ferrocene-unit at the 1,3-or 1,3,5-positions of aromatic rings. The donor molecules with TTF-units have been synthesized using the palladium-catalyzed cross-coupling reaction of tetrathiafulvalenyltin with halogenated benzene derivatives. The dication diradicals and trication triradicals prepared from the TTF-donors show conductivity like a semi-conductor. However, these radical salts indicate almost no ferromagnetic interaction between radical centers. The donor molecules with ferrocene-units have been synthesized by the palladium-catalyzed cross-coupling reaction of ferrocenylzinc reagent with halogenated benzene derivatives. This reaction easily produces the products in a one-pot procedure. The dication diradical or trication triradical salts of the ferrocenedonor show some interaction of ferrocenyl irons. However, the conductivity measurements of this system indicate that the radical salts are a insulator.

Research Products

• [Publications] Masahiko Iyoda: "Synthesis of the Tris(9-fluorenylidene)cyclopropane Dianion and Related Dianions:3 Radialenes with Novel Electronic Properties" Angew.Chem.,Int.Ed.Engl.32. 89-90 (1993)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] Masato Yoshida: "Convenient Preparation and Michael Reactions of 4-Fluoroalkylated But-2-en-4-olides" J.Chem.Soc.,Perkin Trans.1. 501-504 (1993)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] Masato Yoshida: "Reaction of C_<60> with Diacyl Peroxides Containing Perfluoroalkyl Groups.The First Example of Electron Transfer Reaction via C_<60>^+" Tetrahedron Letters. 34. 7629-7632 (1993)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] Hideki Saitoh: "Crystal Structures of the Room-Temperature Phase of 4,4''-Difluoro-p-terphenyl and 4,4'''-Difluoro-p-quaterphenyl" Bull.Chem.Soc.Jpn.66. 2847-2853 (1993)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] Masahiko Iyoda: "Synthesis of (1,5-Diazabicyclo 4.3.0 nonan-2-ylidene-pentacarbonylchromium and -tungsten Using Reaction of Carbene Complexes with 6-Membered Hydrazine" Chem.Lett.777-778 (1994)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] Masahiko Iyoda: "Synthesis and Properties of Platinum Complexes of Fullerenes(C_<60> and C_<70>)" Fullerene Science and Technology. (in press). (1994)
  • Description: 「研究成果報告書概要(和文)」より
• [Publications] Masahiko Iyoda, Hiroyuki Kurata, Masaji Oda, Chiaki Okubo, and Kichisuke Nishimoto: ""Synthesis of the Tris(9-fluorenylidene)cyclopropane. Dianion and Related Dianions : [3]Radialenes with Novel Electronic Properties"" Angew.Chem., Int.Ed.Engl.32. 89-90 (1993)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] Hiroyuki Higuchi, Masao Kondo, Hiroko Yonehara, Juro Ojima, and Masahiko Iyoda: ""Synthesis of 1-(2,2-Dicyanovinyl)-, 1-(2,4,4-Tricyano-1,3-butadienyl)-, 1,6-Bis(2,2-dicyanovinyl)-1,3,5-cycloheptatriene and Their Vinylogs"" Bull.Chem.Soc.Jpn.66. 275-281 (1993)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] Hiroyuki Higuchi, Hiroyuki Yamamoto, Masahiko Iyoda, Masato Yoshida, and Gaku Yamamoto: ""Synthesis of Methano-bridged Tetradehydro[36]annulene"" J.Chem.Soc., Perkin Trans.1. 983-986 (1993)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] Masato Yoshida, Rihoko Imai, Yoji Komatsu, Yoshihiro Morinaga, Norimasa Kamigata, and Masahiko Iyoda: ""Convenient Preparation and Michael Reactions of 4-Fluoroalkylated But-2-en-4-olides"" J.Chem.Soc., Perkin Trans.1. 501 (1993)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] Masato Yoshida, Yoshihiro Morinaga, Masahiko Iyoda, Koichi Kikuchi, Isao Ikemoto, and Yohji Achiba: ""Reaction of C_<60> with Diacyl Peroxides Containing Perfluoroalkyl Groups. The First Example of Electron Transfer Reaction via C60^+ in solution"" Tetrahedron Lett.34. 7629-7632 (1993)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] Hideki Saitoh, Kazuya Saito, Yasuhisa Yamamura, Haruo Matsuyama, Koichi Kikuchi, Masahiko Iyoda, and Isao Ikemoto: ""Crystal Structures of the Room-Temperature Phase of 4,4" -Difluoro-p-terphenyl and 4,4" - Difluoro-p-quaterphenyl"" Bull.Chem.Soc.Jpn.66. 2847-2853 (1993)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] Masahiko Iyoda, Li Zhao, and Haruo Matsuyama: ""Synthesis of (1,5-Diazabicyclo[4.3.0]nonan-2-ylidene)pentacarbonylchromium and -tungsten Using Reaction of 2-Unsaturated Carbene Complexes with 6-Membered Hydrazine"" Chem.Lett.777 (1994)
  • Description: 「研究成果報告書概要(欧文)」より
• [Publications] Masahiko Iyoda, Yoshio Ogawa, Haruo Matsuyama, Hisanori Ueno, Koichi Kikuchi, Isao Ikemoto, and Yohji Achiba: ""Synthesis and Properties of Platinum Complexes of Fullerenes (C_<60> and C_<70>)"" Fullerene Science and Technology. in press.
  • Description: 「研究成果報告書概要(欧文)」より