title: Structural and transport properties of neutral radical crystals of CoIII(tmp)(CN)2(tmp = 5,10,15,20-tetramethylporphyrinato) and the CN-bridged polymer [CoIII(tmp)(CN)]n.
abstract: An axially ligated Co(tmp) (tmp = 5,10,15,20-tetramethylporphyrinato) anion, [CoIII(tmp)(CN)2]-, has been prepared and subjected to electrochemical oxidation to obtain the open shell tmp π-ligand. With acetone as the solvent, solvent-free neutral radical crystals of CoIII(tmp)(CN)2are obtained, whereas solvent-inclusive crystals of CoIII(tmp)(CN)2·2CH3CN are obtained with CH3CN as the solvent. In both crystals, the open shell tmp ring deforms into a ruffled form, which makes the π-π interactions in the crystal weak. Thus, the electrical conductivity is low, and the crystals behave as semiconductors with a room temperature resistivity of 106Ω cm and an activation energy of about 0.3 eV. When the solvent is acetone, non-oxidized crystals of the CN-bridged polymer {[CoIII(tmp)(CN)](acetone)}nare obtained as a byproduct. The closed shell tmp ring deforms into a ruffled form, and there π-π interactions in the crystal are negligible. The room temperature resistivity is rather high at about 108Ω cm.
authors.affiliation: Graduate School of Chemical Sciences and Engineering, Hokkaido University, Sapporo 060-0810, Japan.
authors.forename: Masashi
authors.initials: M
authors.lastname: Kurokawa
authors.affiliation: Department of Chemistry, Graduate School of Science, Hokkaido University, Sapporo 060-0810, Japan.
authors.forename: Judy Fe F
authors.initials: JF
authors.lastname: Jose-Larong
authors.affiliation: Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo 060-0810, Japan. inabe@sci.hokudai.ac.jp.
authors.forename: Hiroyuki
authors.identifier: http://orcid.org/0000-0002-7138-780X
authors.initials: H
authors.lastname: Hasegawa
authors.affiliation: Graduate School of Chemical Sciences and Engineering, Hokkaido University, Sapporo 060-0810, Japan and Department of Chemistry, Graduate School of Science, Hokkaido University, Sapporo 060-0810, Japan and Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo 060-0810, Japan. inabe@sci.hokudai.ac.jp.
authors.forename: Yukihiro
authors.initials: Y
authors.lastname: Takahashi
authors.affiliation: Graduate School of Chemical Sciences and Engineering, Hokkaido University, Sapporo 060-0810, Japan and Department of Chemistry, Graduate School of Science, Hokkaido University, Sapporo 060-0810, Japan and Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo 060-0810, Japan. inabe@sci.hokudai.ac.jp.
authors.forename: Jun
authors.initials: J
authors.lastname: Harada
authors.affiliation: Graduate School of Chemical Sciences and Engineering, Hokkaido University, Sapporo 060-0810, Japan and Department of Chemistry, Graduate School of Science, Hokkaido University, Sapporo 060-0810, Japan and Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo 060-0810, Japan. inabe@sci.hokudai.ac.jp.
authors.forename: Tamotsu
authors.identifier: http://orcid.org/0000-0003-2891-1079
authors.initials: T
authors.lastname: Inabe