An electrically conducting molecular crystal composed of a magnetic iron(<scp>iii</scp>) complex (<i>S</i> = 1/2) with a large aromatic ligand, 1,2-naphthlalocyanine (<i>C</i><sub>4h</sub> isomer): towards the development of molecular spintronics
An electrically conducting molecular crystal composed of a magnetic iron(<scp>iii</scp>) complex (<i>S</i> = 1/2) with a large aromatic ligand, 1,2-naphthlalocyanine (<i>C</i><sub>4h</sub> isomer): towards the development of molecular spintronics
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一种导电分子晶体，由磁性铁 (<scp>iii</scp>) 络合物 (<i>S</i> = 1/2) 和大芳香族配体 1,2-萘花青 (<i>
DOI：
10.1039/d1dt00588j
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发表时间：
2021
影响因子：
4
通讯作者：
Matsuda Masaki
中科院分区：
文献类型：
--
作者：
Yamaguchi Masayuki;Iwamura Sayaka;Mine Kosuke;Murakawa Hiroshi;Hanasaki Noriaki;Matsuda Masaki
分子自旋电子学在第二代自旋电子学器件的研究中得到了广泛的关注。因此，制备了具有强π-d相互作用的新型配位化合物Ph4P[FeIII(1,2- nc)(CN)2]2 （Ph4P =四苯基磷和1,2-萘菁的C4h异构体）的导电分子晶体Ph4P[FeIII(1,2- nc) [CN]2]。此外，它是一个混合价化合物，在传导路径中心的局部自旋为S = 1/2。晶体结构分析表明，Ph4P[FeIII(1,2- nc)(CN)2]2与其非磁性类似物Ph4P[CoIII(1,2- nc)(CN)2]2具有相同的结构，但具有更高的电阻率，表明[FeIII(1,2- nc)(CN)2]单元存在较强的分子内π-d相互作用。虽然π-传导电子与feii -d自旋之间的磁相互作用（π-d相互作用）是产生负磁电阻效应的关键，但Ph4P[FeIII(1,2- nc)(CN)2]2的负磁电阻效应明显小于Ph4P[FeIII(Pc)(CN)2]2（−32%）和Ph4P[FeIII(tbp)(CN)2]2（−13%）类似物（Pc =酞菁和tbp =四苯并卟啉）。Ph4P[FeIII(Pc)(CN)2]2的这种小的负磁阻效应可归因于其d自旋之间弱的分子间反铁磁相互作用。因此，本研究表明，构建增强分子间反铁磁相互作用的分子设计是增强负磁阻效应的关键。
The field of molecular spintronics has gained significant attention for the development of second-generation spintronic devices. Therefore, an electrically conducting molecular crystal, Ph4P[FeIII(1,2-Nc)(CN)2]2 (Ph4P = tetraphenylphosphonium and 1,2-Nc = C4h isomer of 1,2-naphthalocyanine), was fabricated as a new coordination compound with a strong π–d interaction. Furthermore, it is a mixed-valence compound with a local spin of S = 1/2 at the center of the conduction path. Crystal structure analysis revealed that Ph4P[FeIII(1,2-Nc)(CN)2]2 was isostructural to its non-magnetic analogue Ph4P[CoIII(1,2-Nc)(CN)2]2 but possessed higher electrical resistivity, indicating that the strong intramolecular π–d interaction is present in the [FeIII(1,2-Nc)(CN)2] unit. Although the magnetic interaction between π-conduction electrons and FeIII-d spins (π–d interaction) is crucial for the emergence of a negative magnetoresistance effect, the negative magnetoresistance effect of Ph4P[FeIII(1,2-Nc)(CN)2]2 was significantly smaller (−6% at 30 K under a static 9 T magnetic field) than those of Ph4P[FeIII(Pc)(CN)2]2 (−32%) and Ph4P[FeIII(tbp)(CN)2]2 (−13%) analogues (Pc = phthalocyanine and tbp = tetrabenzoporphyrin). This small negative magnetoresistance effect of Ph4P[FeIII(Pc)(CN)2]2 could be ascribed to the weak intermolecular antiferromagnetic interaction between its d spins. Hence, this study showed that constructing a molecular design for strengthening the intermolecular antiferromagnetic interaction is key to enhancing the negative magnetoresistance effect.