Benzenetriimide‐Based Molecular Conductor with Antiferro‐ to Ferromagnetic Switching Induced by Structural Change of π‐stacked Array
Benzenetriimide‐Based Molecular Conductor with Antiferro‐ to Ferromagnetic Switching Induced by Structural Change of π‐stacked Array
复制标题
π堆叠阵列结构变化引起的具有反铁磁到铁磁转换的苯三亚胺基分子导体
DOI：
10.1002/cphc.202200322
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发表时间：
2022
期刊：
影响因子：
2.9
通讯作者：
Iguchi Hiroaki
中科院分区：
文献类型：
--
作者：
Koyama Shohei;Horii Yoji;Sato Tetsu;Takaishi Shinya;Hoshino Norihisa;Akutagawa Tomoyuki;Iguchi Hiroaki
苯三酰亚胺（BTI）是一种很有前途的材料化学结构单元，由于其特有的三重对称性和氧化还原性质，而对其导电和磁性知之甚少。在本研究中，我们合成了三种基于N，N '，N“-三甲基苯三酰亚胺（BTI-Me）的电荷转移配合物。其中一个复合物含有BTI-Me自由基阴离子的孤立二聚体（BTI-Me −），而另外两个复合物含有形式电荷为−0.5的BTI-Me的无限π堆叠阵列。后两种配合物没有表现出金属行为，但表现出半导体行为，这可能是由于一维电子系统中的特征绝缘，即所谓的电荷有序和二聚体-莫特绝缘。二聚体-Mott态的复合物的磁化率表现出从反铁磁到铁磁自旋态的不寻常转变，磁滞回线为15 K，来自130 K附近的结构相变。 这些性质也得到了DFT计算的支持。
Benzenetriimide (BTI) is a promising building block for materials chemistry due to its characteristic 3‐fold symmetry and redox properties, whereas little is known about its conductive and magnetic properties. In this study, we synthesized three charge‐transfer complexes based onN,N’,N’’‐trimethylbenzenetriimide (BTI‐Me). One of the complexes contains isolated dimers of BTI‐Me radical anion (BTI‐Me⋅−), while the other two have the infinite π‐stacked array of BTI‐Me with the formal charge of −0.5. The latter two complexes did not show metallic behavior but showed semiconducting behavior probably due to the characteristic insulation in one‐dimensional electron system, so‐called charge ordering and dimer‐Mott insulation. The magnetic susceptibility of the complex in dimer‐Mott state exhibits an unusual transition from antiferromagnetic to ferromagnetic spin states with the hysteresis loop of 15 K derived from the structural phase transition around 130 K. These properties were also supported by DFT calculations.