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Structural and transport properties of neutral radical crystals of Co-III(tmp)(CN)(2) (tmp=5,10,15,20-tetramethylporphyrinato) and the CN-bridged polymer [Co-III( tmp)(CN)](n)

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Title: Structural and transport properties of neutral radical crystals of Co-III(tmp)(CN)(2) (tmp=5,10,15,20-tetramethylporphyrinato) and the CN-bridged polymer [Co-III( tmp)(CN)](n)
Authors: Kurokawa, Masashi Browse this author
Jose-Larong, Judy Fe F. Browse this author
Hasegawa, Hiroyuki Browse this author →KAKEN DB
Takahashi, Yukihiro Browse this author →KAKEN DB
Harada, Jun Browse this author →KAKEN DB
Inabe, Tamotsu Browse this author →KAKEN DB
Issue Date: 7-Apr-2017
Publisher: Royal Society of Chemistry
Journal Title: Dalton transactions
Volume: 46
Issue: 13
Start Page: 4422
End Page: 4429
Publisher DOI: 10.1039/c6dt04418b
PMID: 28300234
Abstract: An axially ligated Co(tmp) (tmp = 5,10,15,20-tetramethylporphyrinato) anion, [Co-III(tmp)(CN)(2)](-), has been prepared and subjected to electrochemical oxidation to obtain the open shell tmp pi-ligand. With acetone as the solvent, solvent-free neutral radical crystals of Co-III(tmp)(CN)(2) are obtained, whereas solvent-inclusive crystals of Co-III(tmp)(CN)(2)center dot 2CH(3)CN are obtained with CH3CN as the solvent. In both crystals, the open shell tmp ring deforms into a ruffled form, which makes the pi-pi interactions in the crystal weak. Thus, the electrical conductivity is low, and the crystals behave as semiconductors with a room temperature resistivity of 10(6) Omega cm and an activation energy of about 0.3 eV. When the solvent is acetone, non-oxidized crystals of the CN-bridged polymer {[Co-III(tmp)(CN)](acetone)}(n) are obtained as a byproduct. The closed shell tmp ring deforms into a ruffled form, and there pi-pi interactions in the crystal are negligible. The room temperature resistivity is rather high at about 10(8) Omega cm.
Type: article (author version)
URI: http://hdl.handle.net/2115/68739
Appears in Collections:理学院・理学研究院 (Graduate School of Science / Faculty of Science) > 雑誌発表論文等 (Peer-reviewed Journal Articles, etc)

Submitter: 稲辺 保

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