(nBu4N)[Ni(dmstfdt)2]: A Planar Nickel Coordination Complex with an Extended-TTF Ligand Exhibiting Metallic Conduction, Metal−Insulator Transition, and Weak Ferromagnetism
(nBu4N)[Ni(dmstfdt)2]: A Planar Nickel Coordination Complex with an Extended-TTF Ligand Exhibiting Metallic Conduction, Metal−Insulator Transition, and Weak Ferromagnetism
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DOI：
10.1021/cm062131q
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发表时间：
2007-01
影响因子：
8.6
通讯作者：
E. Fujiwara;Kimiko Yamamoto;M. Shimamura;Biao Zhou;A. Kobayashi;Kazuyuki Takahashi;Y. Okano;Hengbo Cui;H. Kobayashi
中科院分区：
文献类型：
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作者：
E. Fujiwara;Kimiko Yamamoto;M. Shimamura;Biao Zhou;A. Kobayashi;Kazuyuki Takahashi;Y. Okano;Hengbo Cui;H. Kobayashi
具有扩展TTF配体的镍配合物的1：1四丁基铵盐（nBu 4 N）[Ni（dmstfdt）2]（dmstfdt = dimethyldiselenadithiafulvalenedithiolate）（1）是一种独特的矛盾分子体系，在室温以上表现出弱金属导电性，在低温下表现出弱铁磁性。它的X射线结构由两个独立的[Ni（dmstfdt）2]-（A和B）和两个nBu 4 N+组成。准平面阴离子沿着分子并排方向以锯齿形-ABA 'B'-方式排列，分子平面的二面角为42.6°。紧束缚能带结构的计算，基于扩展的休克尔近似估计的转移积分，提出了三维电子和空穴费米表面，这是一致的，尽管1：1的化学计量的复杂的观察到的弱金属导电室温附近。在147 K，1显示了一个尖锐的绝缘过渡与本地化的一个电子上的每个镍复杂。
The 1:1 tetrabutylammonium salt of a nickel complex with an extended-TTF ligand, (nBu4N)[Ni(dmstfdt)2] (dmstfdt = dimethyldiselenadithiafulvalenedithiolate) (1) is a unique ambivalent molecular system exhibiting weakly metallic conduction above room temperature and a weak ferromagnetism at low temperature. Its X−ray structure consists of two independent [Ni(dmstfdt)2]- (A and B) and two nBu4N+ in the unit cell. The pseudo-planar anions are arranged in a zigzag -ABA‘B‘- manner along the molecular side-by-side direction with a dihedral angle of the molecular planes of 42.6°. The tight-binding band structure calculation, based on transfer integrals estimated by the extended Huckel approximation, presents both three-dimensional electron and hole Fermi surfaces, which is consistent with the observed weakly metallic conduction around room-temperature despite the 1:1 stoichiometry of the complex. At 147 K, 1 shows a sharp insulating transition associated with the localization of one electron on each nickel compl...