- 【Updated on May 12, 2025】 Integration of CiNii Dissertations and CiNii Books into CiNii Research
- Trial version of CiNii Research Knowledge Graph Search feature is available on CiNii Labs
- Suspension and deletion of data provided by Nikkei BP
- Regarding the recording of “Research Data” and “Evidence Data”
Biferrocene−M(mnt)<sub>2</sub>Charge-Transfer Complexes (M = Ni, Co; mnt = Maleonitriledithiolate). Structure, Valence States, and Magnetic Properties
-
- Tomoyuki Mochida
- Department of Chemistry, Faculty of Science, Toho University, Miyama, Funabashi, Chiba 274-8510, Japan, Department of Physics, Faculty of Science, Toho University, Miyama, Funabashi, Chiba 274-8510, Japan, and Institute for Solid State Physics, The University of Tokyo, Kashiwanoha, Kashiwa-shi, Chiba 277-8581, Japan
-
- Kousuke Takazawa
- Department of Chemistry, Faculty of Science, Toho University, Miyama, Funabashi, Chiba 274-8510, Japan, Department of Physics, Faculty of Science, Toho University, Miyama, Funabashi, Chiba 274-8510, Japan, and Institute for Solid State Physics, The University of Tokyo, Kashiwanoha, Kashiwa-shi, Chiba 277-8581, Japan
-
- Hideaki Matsui
- Department of Chemistry, Faculty of Science, Toho University, Miyama, Funabashi, Chiba 274-8510, Japan, Department of Physics, Faculty of Science, Toho University, Miyama, Funabashi, Chiba 274-8510, Japan, and Institute for Solid State Physics, The University of Tokyo, Kashiwanoha, Kashiwa-shi, Chiba 277-8581, Japan
-
- Masashi Takahashi
- Department of Chemistry, Faculty of Science, Toho University, Miyama, Funabashi, Chiba 274-8510, Japan, Department of Physics, Faculty of Science, Toho University, Miyama, Funabashi, Chiba 274-8510, Japan, and Institute for Solid State Physics, The University of Tokyo, Kashiwanoha, Kashiwa-shi, Chiba 277-8581, Japan
-
- Masuo Takeda
- Department of Chemistry, Faculty of Science, Toho University, Miyama, Funabashi, Chiba 274-8510, Japan, Department of Physics, Faculty of Science, Toho University, Miyama, Funabashi, Chiba 274-8510, Japan, and Institute for Solid State Physics, The University of Tokyo, Kashiwanoha, Kashiwa-shi, Chiba 277-8581, Japan
-
- Michiko Sato
- Department of Chemistry, Faculty of Science, Toho University, Miyama, Funabashi, Chiba 274-8510, Japan, Department of Physics, Faculty of Science, Toho University, Miyama, Funabashi, Chiba 274-8510, Japan, and Institute for Solid State Physics, The University of Tokyo, Kashiwanoha, Kashiwa-shi, Chiba 277-8581, Japan
-
- Yutaka Nishio
- Department of Chemistry, Faculty of Science, Toho University, Miyama, Funabashi, Chiba 274-8510, Japan, Department of Physics, Faculty of Science, Toho University, Miyama, Funabashi, Chiba 274-8510, Japan, and Institute for Solid State Physics, The University of Tokyo, Kashiwanoha, Kashiwa-shi, Chiba 277-8581, Japan
-
- Koji Kajita
- Department of Chemistry, Faculty of Science, Toho University, Miyama, Funabashi, Chiba 274-8510, Japan, Department of Physics, Faculty of Science, Toho University, Miyama, Funabashi, Chiba 274-8510, Japan, and Institute for Solid State Physics, The University of Tokyo, Kashiwanoha, Kashiwa-shi, Chiba 277-8581, Japan
-
- Hatsumi Mori
- Department of Chemistry, Faculty of Science, Toho University, Miyama, Funabashi, Chiba 274-8510, Japan, Department of Physics, Faculty of Science, Toho University, Miyama, Funabashi, Chiba 274-8510, Japan, and Institute for Solid State Physics, The University of Tokyo, Kashiwanoha, Kashiwa-shi, Chiba 277-8581, Japan
Search this article
Description
Charge-transfer salts of branched-alkyl biferrocenes, (1',1' ''-R2-1,1' '-biferrocene)[Ni(mnt)2] (1a, R = isopropyl; 2a, R = dineopentyl) and (1',1' ''-R2-1,1' '-biferrocene)2[Co(mnt)2]2 (1b, R = isopropyl; 2b, R = dineopentyl), were prepared. Their valence states were investigated using X-ray crystallography and Mössbauer spectroscopy. Complexes 1a and 1b show segregated-stack crystal structures that contain columns of acceptors, whereas structures of 2a and 2b, which contain bulky donors, are rather discrete. All of the complexes contain mixed-valent biferrocenium monocations. A two-step valence transition was found in complex 1a. The crystal contains two crystallographically independent cations: one undergoes valence localization below room temperature; the other undergoes valence localization below ca. 130 K. The former transition is derived from asymmetry of the crystal environment around the cation, whereas the latter one is caused by symmetry lowering coupled with a spin-Peierls transition (T(C) = 133.2 K) associated with the dimerization of the acceptors. This compound was found to exhibit a dielectric response based on valence tautomerization. Other complexes (1b, 2a, and 2b) show a valence-trapped state. In all complexes, charge localization was found to occur through local electrostatic interactions between the donor's cationic moiety and the acceptor's electronegative moieties.
Journal
-
- Inorganic Chemistry
-
Inorganic Chemistry 44 (23), 8628-8641, 2005-10-07
American Chemical Society (ACS)
