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
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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CoIII(tmp)(CN)2 (tmp = 5,10,15,20-四甲基卟啉)和 CN 桥聚合物 [CoIII(tmp)(CN)]n 的中性自由基晶体的结构和传输特性
DOI：
10.1039/c6dt04418b
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发表时间：
2017
期刊：
影响因子：
--
通讯作者：
and T. Inabe
中科院分区：
文献类型：
--
作者：
M. Kurokawa;J. F. F. Jose-Larong;H. Hasegawa;Y. Takahashi;J. Harada;and T. Inabe
合成了轴向配位的Co（tmp）（tmp = 5，10，15，20-四甲基卟啉）阴离子[CoIII（tmp）（CN）2]−，并通过电化学氧化得到了开壳层的TMP π-配体.以丙酮为溶剂，得到了无溶剂的CoIII（tmp）（CN）2中性自由基晶体，而以CH 3CN为溶剂，得到了含溶剂的CoIII（tmp）（CN）2·2CH 3CN晶体。在这两种晶体中，开壳层TMP环变形为褶皱形式，这使得晶体中的π-π相互作用变弱。因此，电导率低，晶体表现为半导体，室温电阻率为106 Ω cm，活化能约为0.3 eV。当溶剂是丙酮时，作为副产物获得CN-桥连聚合物{[CoIII（tmp）（CN）]（丙酮）}n的非氧化晶体。晶体中存在的π-π相互作用可以忽略不计。室温电阻率较高，约为108 Ω cm。
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.