An electron-transfer ferromagnet with T(c) = 107 K based on a three-dimensional [Ru2]2/TCNQ system.
An electron-transfer ferromagnet with T(c) = 107 K based on a three-dimensional [Ru2]2/TCNQ system.
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DOI：
10.1002/anie.200802574
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发表时间：
2008-09
影响因子：
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通讯作者：
Natsuko Motokawa;H. Miyasaka;M. Yamashita;K. Dunbar
中科院分区：
文献类型：
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作者：
Natsuko Motokawa;H. Miyasaka;M. Yamashita;K. Dunbar
设计具有有效电子通讯的dπ-pπ分子体系是无机化学领域的一个长期目标。这项研究的指导原则是对1969年发现的Creutz-Taube离子[（H3 N）5 Ru（μ-pyz）Ru（NH3）5] 5+（pyz=吡嗪）[1]以及随后的相关化合物[2]的开创性研究提供的，这些化合物通过有机桥接配体在混合价金属离子之间进行电荷转移相互作用。进行了各种实验研究以评估电子转移动力学，并由Hush，[3] Marcus和Sutin [4]等人开发了动力学和热力学方法的理论解释。[5]在当前工作的背景下，我们还注意到Crutchley及其同事的重要贡献，他们探索了由1，4-二氰胺基苯二价阴离子（Diclitazinobenzene 2benzene）或其取代衍生物之一桥接的双核钌（III）配合物中的电子转移过程。[6]有趣的是，这类化合物通过Dicyd桥的pπ轨道在RuIII S= 1/2自旋之间表现出强烈的分子内磁耦合，其中J超过400 cm 3 - 1，与高度共轭的π-d网络密切相关，在Robin-Day尺度上被归类为II类或III类行为。[7]这种系统的一个关键设计要素是1：2单电子给体的比例（D，即Dicyd）的单电子受体（A，即，RuIII离子），其可导致[A β-D+-AA-D+-A β]型电子转移共振，与Creutz-Taube离子以两种共振形式存在的方式大致相同[RuIII-pyz-RuII $ RuII-pyz-RuIII]我们的研究是针对具有dπ/pπ共轭的配位骨架固体的合成，目标是实现混合磁性和导电性能。简而言之，我们在这一领域的研究可以在概念上表达为“将Creutz-Taube分子扩展到更高的维度，
The design of dπ–pπ molecular systems with efficient electronic communication is a long-standing goal in the field of inorganic chemistry. Guiding principles for this research are provided by the seminal studies on the Creutz–Taube ion,[(H3N) 5Ru (μ-pyz) Ru (NH3) 5] 5+(pyz= pyrazine), discovered in 1969,[1] as well as subsequent related compounds [2] that undergo charge-transfer interactions between mixed-valent metal ions through an organic bridging ligand. Various experimental investigations to evaluate the electron-transfer dynamics were undertaken and theoretical interpretations from kinetic and, thermodynamic approaches were developed by Hush,[3] Marcus and Sutin,[4] and others.[5] In the context of the current work, we also note the important contributions of Crutchley and co-workers, who explored electron-transfer processes in dinuclear ruthenium-(III) complexes bridged by the 1, 4-dicyanamidobenzene dianion (Dicyd2À) or one of its substituted derivatives.[6] Interestingly, this class of compounds demonstrated strong intramolecular magnetic coupling between RuIII S= 1/2 spins via the pπ orbital of the Dicyd bridge with J exceeding 400 cmÀ1 closely associated with a highly conjugated π–d network, classified as Class II or III behavior on the Robin–Day scale.[7] A crucial design ingredient for such systems is a 1: 2 ratio of the one-electron donor (D, ie, Dicyd) to the oneelectron acceptor (A, ie, a RuIII ion) that can lead to an electron-transfer resonance of type [AÀ–D+–AA–D+–AÀ], in much the same fashion that the Creutz–Taube ion can exist in two resonance forms [RuIII-pyz-RuII $ RuII-pyz-RuIII].Our research is directed at the synthesis of coordination framework solids with dπ/pπ conjugation with the goal of achieving hybrid magnetic and conducting properties. In short, our research in this area can be expressed conceptually as “expanding the Creutz–Taube molecule to higher dimen-