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Conduction Mechanism of Metallic Organic Conductor with 1 : 1 Composition

1:1组成的金属有机导体的导电机理

基本信息

批准号：
10440204
负责人：
MORI Takehiko
金额：
$ 8.58万
依托单位：
Tokyo Institute of Technology
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
1998
资助国家：
日本
起止时间：
1998 至 1999
项目状态：
已结题

项目摘要

It has been widely believed that organic conductors with 1:1 composition are insulators. Nonetheless, we have found that an organic conductor (TTM-TTP)IィイD23ィエD2 exhibites metallic conductivity down to 160 K, and that the insulating state below this temperature is paramagnetic. The re-investigation of magnetic susceptibility together with the measurements of ィイD113ィエD1C-NMR and low-temperature X-ray diffraction have, however, revealed that the low temperature state is a non magnetic insulator with two-fold lattice modulation in the stacking direction. Furthermore, we have prepared two kinds of new metallic 1:1 salts, (TTM-TTP)[C(CN)ィイD23ィエD2] and (TTM-TTP)FeClィイD22ィエD2BrィイD22ィエD2. These salts have one-dimensional uniform, columns, and are metallic down to 70 K and 160 K, respectively. Five insulating 1:1 salts with AuIィイD22ィエD2, AuBrィイD22ィエD2, HgIィイD23ィエD2(TCE), FeClィイD24ィエD2(PhCl), and FeBrィイD24ィエD2(PhCl), that have dimerized columns, have been obtained as well. ESR investigation has been carried out for (DTM-TTP)(TCNQ)(TCE) and (TMET-TTP)ィイD22ィエD2(TCNQ). The former complex has a nonmagnetic insulating state below 100 K, whereas the insulating phase of the latter complex below 120 K is paramagnetic. This difference is attributed to the structures; the former complex has one-dimensional segregated stacks, and the latter has a two-dimansional θ-type donor arrangement, in which TCNQ works as an isolated anion. These investigations indicate that the origin of the insulating state in the 1:1 organic conductors are not correlation, but one-dimensional instability such as CDW formation.

人们普遍认为组成为1：1的有机导体是绝缘体。然而，我们发现有机导体(TTm-Ttp)IィイD23ィエD2在160K以下表现出金属导电性，并且低于这一温度的绝缘态是顺磁性的。磁化率的重新研究，结合ィイD113ィエD1C核磁共振和低温X射线衍射谱的测量，揭示了低温状态是一个沿堆积方向具有双重晶格调制的非磁性绝缘体。此外，我们还合成了两种新的金属1：1盐，(Ttm-Ttp)[C(CN)ィイD23ィエD2]和(Ttm-Ttp)FeClィイD22ィエD2BrD22ィイD22ィエD2。这些盐具有一维均匀的柱状结构，并分别在70K和160K以下为金属盐。还得到了5种具有二聚化柱的绝缘1：1盐，分别为AuIィイD22ィエD2、AuBrRィイD22ィエD2、HgIィイD23ィエD2(三氯乙烯)、FeClFeClD24ィイD2(PPhl)和FeBrD24ィエD2(PPhl)。对(dTM-TTP)(TCNQ)(TCE)和(TMET-TTP)ィイD22ィエD2(TCNQ)进行了电子自旋共振研究。前者在100K以下为非磁性绝缘态，而后者在120K以下为顺磁性。这种差异归因于结构；前者具有一维分离堆栈，后者具有二维θ类型的施主排列，其中TCNQ作为孤立的阴离子工作。这些研究表明，1：1有机导体中绝缘态的起源不是关联的，而是一维不稳定的，如CDW的形成。