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Issue 13, 2017
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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

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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)2 are 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 106 Ω 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)}n are 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 108 Ω cm.

Graphical abstract: 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

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Publication details

The article was received on 22 Nov 2016, accepted on 05 Mar 2017 and first published on 06 Mar 2017


Article type: Paper
DOI: 10.1039/C6DT04418B
Citation: Dalton Trans., 2017,46, 4422-4429
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    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

    M. Kurokawa, J. F. F. Jose-Larong, H. Hasegawa, Y. Takahashi, J. Harada and T. Inabe, Dalton Trans., 2017, 46, 4422
    DOI: 10.1039/C6DT04418B

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