Highly Conductive [3 x n] Gold-Ion Clusters Enclosed within Self-Assembled Cages
Highly Conductive [3 x n] Gold-Ion Clusters Enclosed within Self-Assembled Cages
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DOI：
10.1002/anie.201301665
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发表时间：
2013-01-01
影响因子：
16.6
通讯作者：
Watanabe, Satoshi
中科院分区：
文献类型：
--
作者：
Kiguchi, Manabu;Inatomi, Junichi;Watanabe, Satoshi
金属原子线在单分子水平上的电子导电性越来越受到人们的关注，因为它们的量子化电学性质适用于超小型器件中的导线。[1-3]相比之下，金属离子线的单分子导电性从未被研究过，金属离子线是导电的还是绝缘的一直是一个有争议的问题，[4-6]因为在纳米间隙电极之间制造具有固定横截面和长度的金属离子阵列是不容易的。近年来，研究人员开发了几种制备有序金属离子阵列多核配合物的有效方法。其中，封闭在自组装笼1中的[3n]金离子簇（图1）特别有趣，因为堆叠数n是由柱配体的长度唯一决定的(4)。为了期望通过金属离子阵列的有效电子传输，测量了通过[3n]金离子簇(2)n （n= 1、2或3）堆叠的单分子电子电导率。笼，1使金属离子在腔内以[3n]的方式保持高度有序，是容纳π堆叠分子和评估其电子传输性质的优秀框架。[7,8]我们证明了金属离子阵列具有高导电性，电子传递与金属原子线相当，绝对电导值远远大于金属连接的有机线。我们通过从头算输运计算证实了[3n] AuI离子簇适合于高电导，在较长的输运距离上衰减可以忽略不计。我们计算了相应模型阵列的电导，3·（2a） n·3 (n= 1-4)（见辅助资料）。图2显示了计算出的电导值
There is an increasing interest in the electron conductivity of metal-atom wires at the single-molecule level because of their quantized electric properties applicable to conducting wires in ultra-small devices.[1–3] In contrast, the single-molecular conductivity of metal-ion wires has never been studied and whether the metal-ion wires are conductive or insulating has been a matter of debate,[4–6] because creating metal-ion arrays with a fixed cross section and length between nanogap electrodes is nontrivial. In recent years, several efficient methods have been developed for preparing multinuclear complexes with ordered metal-ion arrays. Among them,[3 n] gold-ion clusters, enclosed in self-assembled cages 1 (Figure 1), are particularly interesting because the stacking number n is uniquely determined by the length of the pillar ligand (4). In expectation of efficient electron transport through metal-ion arrays, single-molecular electron conductivity through [3 n] stacks of gold-ion clusters (2) n (n= 1, 2, or 3) was measured. The cages, 1, which keep the metal ions highly ordered in a [3 n] manner within the cavity, are excellent frameworks for accommodating π-stacked molecules and evaluating their electron-transport properties.[7, 8] We show that the metal-ion arrays are highly conductive, the electron transport being comparable to that through metalatom wires and the absolute conductance value being much larger than that of metal-linked organic wires. We confirmed by ab initio transport calculations that the [3 n] AuI ion clusters would be suitable for high conductance with a negligibly small decay over longer transport distances. We calculated the conductance of the corresponding model arrays, 3·(2a) n· 3 (n= 1–4)(See the Supporting Information). Figure 2 shows the calculated conductance values, together