Long-range ordered magnet of a charge-transfer Ru2(4+)/TCNQ two-dimensional network compound.
Long-range ordered magnet of a charge-transfer Ru2(4+)/TCNQ two-dimensional network compound.
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DOI：
10.1021/ja063963s
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发表时间：
2006-08
影响因子：
15
通讯作者：
H. Miyasaka;Toru Izawa;N. Takahashi;M. Yamashita;K. Dunbar
中科院分区：
文献类型：
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作者：
H. Miyasaka;Toru Izawa;N. Takahashi;M. Yamashita;K. Dunbar
合成了[Ru2(O2CCF3)4]与TCNQ或TCNQF4按2：1比例组成的两个等结构二维组合体：[{Ru2(O2CCF3)4}2TCNQ].3(对二甲苯)(1b)和[{Ru2(O2CCF3)4}2TCNQF4].3(对二甲苯)(2)。在1b中，TCNQ部分被指定为中性，因为RU24+单元没有显著的电子转移。因此，1b的磁性可以理解为孤立的RU24+单元的顺磁性，而从RU2单元到2中的TCNQF4分子的完全电荷转移导致电荷离域扩散到2D网络上，并允许发生长程磁序。基于电荷转移D2A型网络体系的共振方案，通过调节[Ru2]4+与TCNQ分子之间的氧化还原关系，合理地设计了第一个成功的RU2-TCNQ体系中电荷转移磁体的例子。
Two isostructural 2D assemblies composed of [Ru2(O2CCF3)4] and TCNQ or TCNQF4 in a 2:1 ratio were synthesized: [{Ru2(O2CCF3)4}2TCNQ].3(p-xylene) (1b) and [{Ru2(O2CCF3)4}2TCNQF4].3(p-xylene) (2). In 1b, the TCNQ moiety is assigned to be neutral because of no significant electron transfer from the Ru24+ units. Therefore, the magnetic property of 1b can be understood to be a paramagnetic nature of the isolated Ru24+ unit, while, a fully charge-transfer from the Ru2 units to the TCNQF4 molecules in 2 leads to charge delocalization spreading over the 2D network and allows a long-range magnetic order to occur. On the basis of an idea of the resonance scheme in charge-transfer D2A network systems, the first successful example of a charge-transferred magnet in the Ru2-TCNQ system was rationally designed by tuning redox between [Ru2]4+ and the TCNQ molecule changing from TCNQ to TCNQF4.