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An electrically conducting crystal composed of an octahedrally ligated porphyrin complex with high-spin iron(iii)†
Dalton Transactions ( IF 4 ) Pub Date : 2018-02-08 00:00:00 , DOI: 10.1039/c7dt04649a Miki Nishi 1, 2, 3, 4 , Ryuta Ishii 4, 5, 6, 7 , Mitsuo Ikeda 4, 5, 6, 7 , Noriaki Hanasaki 4, 5, 6, 7 , Norihisa Hoshino 4, 8, 9, 10 , Tomoyuki Akutagawa 4, 8, 9, 10 , Michinori Sumimoto 4, 11, 12, 13 , Masaki Matsuda 1, 2, 3, 4
Dalton Transactions ( IF 4 ) Pub Date : 2018-02-08 00:00:00 , DOI: 10.1039/c7dt04649a Miki Nishi 1, 2, 3, 4 , Ryuta Ishii 4, 5, 6, 7 , Mitsuo Ikeda 4, 5, 6, 7 , Noriaki Hanasaki 4, 5, 6, 7 , Norihisa Hoshino 4, 8, 9, 10 , Tomoyuki Akutagawa 4, 8, 9, 10 , Michinori Sumimoto 4, 11, 12, 13 , Masaki Matsuda 1, 2, 3, 4
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A porphyrin-based octahedrally ligated complex with high-spin iron(III) was designed, and the resulting electrically conducting crystal TPP[FeIII(tbp)Br2]2 (TPP = tetraphenylphosphonium and tbp = tetrabenzoporphyrin) was synthesised. Although TPP[Fe(tbp)Br2]2 was isostructural to the reported TPP[Fe(Mc)L2]2 systems (Mc = macrocyclic ligands such as phthalocyanine (Pc) or tbp; and L = CN, Cl, or Br), the bond lengths between Fe and ligands in the [Fe(tbp)Br2] unit were evidently longer than those in the other units, because of the different spin states of Fe: high-spin in TPP[Fe(tbp)Br2]2 and low-spin in others. The magnetic anisotropy observed in the low-spin state vanished when the Fe is in the high-spin state. Based on reports for Pc-based systems, the negative magnetoresistance (MR) effect for TPP[Fe(tbp)Br2]2 was expected to be smaller than that for TPP[Fe(tbp)(CN)2]2. However, the former showed a giant negative MR effect similar to or larger than the latter, suggesting that the nature of iron is a crucial factor for the electrical properties of porphyrin-based materials.
中文翻译：
由八面体连接的卟啉配合物与高自旋铁（iii）组成的导电晶体†
设计了具有高自旋铁（III）的基于卟啉的八面体连接配合物，并合成了导电晶体TPP [Fe III（tbp）Br 2 ] 2（TPP =四苯基phosph，tbp =四苯并卟啉）。尽管TPP [Fe（tbp）Br 2 ] 2与报道的TPP [Fe（Mc）L 2 ] 2系统同构（Mc =大环配体，例如酞菁（Pc）或tbp； L = CN，Cl或Br ），[Fe（tbp）Br 2 ]单元中的Fe与配体之间的键长明显长于其他单元中的键长，这是由于Fe的自旋状态不同：TPP [Fe（tbp）Br 2个] 2，其他人则低速旋转。当Fe处于高自旋状态时，在低自旋状态下观察到的磁各向异性消失。根据基于Pc的系统的报告，预计TPP [Fe（tbp）Br 2 ] 2的负磁阻（MR）效应要小于TPP [Fe（tbp）（CN）2 ] 2的负磁阻（MR）效应。但是，前者显示出与后者相似或更大的巨大的负MR效应，这表明铁的性质是卟啉基材料电性能的关键因素。
更新日期：2018-02-08
中文翻译：
由八面体连接的卟啉配合物与高自旋铁（iii）组成的导电晶体†
设计了具有高自旋铁（III）的基于卟啉的八面体连接配合物，并合成了导电晶体TPP [Fe III（tbp）Br 2 ] 2（TPP =四苯基phosph，tbp =四苯并卟啉）。尽管TPP [Fe（tbp）Br 2 ] 2与报道的TPP [Fe（Mc）L 2 ] 2系统同构（Mc =大环配体，例如酞菁（Pc）或tbp； L = CN，Cl或Br ），[Fe（tbp）Br 2 ]单元中的Fe与配体之间的键长明显长于其他单元中的键长，这是由于Fe的自旋状态不同：TPP [Fe（tbp）Br 2个] 2，其他人则低速旋转。当Fe处于高自旋状态时，在低自旋状态下观察到的磁各向异性消失。根据基于Pc的系统的报告，预计TPP [Fe（tbp）Br 2 ] 2的负磁阻（MR）效应要小于TPP [Fe（tbp）（CN）2 ] 2的负磁阻（MR）效应。但是，前者显示出与后者相似或更大的巨大的负MR效应，这表明铁的性质是卟啉基材料电性能的关键因素。
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