Role of Anions Associated with the Formation and Properties of Silver Clusters
Role of Anions Associated with the Formation and Properties of Silver Clusters
复制标题
阴离子与银簇的形成和性质相关的作用
DOI：
10.1021/acs.accounts.5b00007
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发表时间：
2015
影响因子：
18.3
通讯作者：
Kuan-Guan Liu
中科院分区：
文献类型：
--
作者：
Quan-Ming Wang;Yu-Mei Lin;Kuan-Guan Liu
金属团簇以其独特的美学结构和令人着迷的特性而受到人们的广泛关注。与纳米颗粒不同，宏观样品的每一簇都具有明确的结构，具有相同的组成、大小和形状。由于排除了多分散性的缺点，可以建立金属团簇的信息结构-性质关系。高核金属团簇的形成涉及到金属离子有序地组织成复杂的实体。为了实现金属团簇的可控制备，在团簇的形成过程中引入导向剂是有帮助的。为此，阴离子模板被用来指导高核团簇的形成。本文综述了阴离子在各种银簇形成过程中的作用。银离子带正电荷，因此阴离子可以在静电相互作用的基础上控制银团簇的形成，并且得到的团簇的大小和形状可以由模板阴离子决定。此外，由于阴离子是所描述的银团簇中不可或缺的组成部分，因此团簇的物理性质可以通过功能阴离子进行调节。研究了简单无机阴离子和多氧盐在银炔基团簇和银硫酸盐团簇中的模板效应。簇间化合物还描述了阴离子在确定离子对的排列和对正负对应物之间的电子通信作出贡献方面的重要性。阴离子的作用有三方面：(a)阴离子有利于通过平衡金属阳离子的局部正电荷来稳定团簇；(b)阴离子模板可以帮助控制簇产物的大小和形状；(c)阴离子可以通过引入团簇的内在特性而成为影响团簇功能的关键因素。讨论了阴离子取向银簇的电子通信、发光热致变色、单分子磁体和簇间电荷转移等性质。我们希望引起化学家们对阴离子在决定金属配合物，特别是簇的结构和性质方面所起的作用的注意。我们希望这篇文章能激发人们更多的努力，以开发阴离子在各种金属簇体系中的新作用。阴离子在电荷平衡方面的作用远大于反离子，在设计和合成簇基功能材料时应考虑到阴离子的作用。
Metal clusters have been very attractive due to their aesthetic structures and fascinating properties. Different from nanoparticles, each cluster of a macroscopic sample has a well-defined structure with identical composition, size, and shape. As the disadvantages of polydispersity are ruled out, informative structure-property relationships of metal clusters can be established. The formation of a high-nuclearity metal cluster involves the organization of metal ions into a complex entity in an ordered way. To achieve controllable preparation of metal clusters, it is helpful to introduce a directing agent in the formation process of a cluster. To this end, anion templates have been used to direct the formation of high nuclearity clusters. In this Account, the role of anions played in the formation of a variety of silver clusters has been reviewed. Silver ions are positively charged, so anionic species could be utilized to control the formation of silver clusters on the basis of electrostatic interactions, and the size and shape of the resulted clusters can be dictated by the templating anions. In addition, since the anion is an integral component in the silver clusters described, the physical properties of the clusters can be modulated by functional anions. The templating effects of simple inorganic anions and polyoxometales are shown in silver alkynyl clusters and silver thiolate clusters. Intercluster compounds are also described regarding the importance of anions in determining the packing of the ion pairs and making contribution to electron communications between the positive and negative counterparts. The role of the anions is threefold: (a) an anion is advantageous in stabilizing a cluster via balancing local positive charges of the metal cations; (b) an anion template could help control the size and shape of a cluster product; (c) an anion can be a key factor in influencing the function of a cluster through bringing in its intrinsic properties. Properties including electron communication, luminescent thermochromism, single-molecule magnet, and intercluster charge transfer associated with anion-directed silver clusters have been discussed. We intend to attract chemists' attention to the role that anions could play in determining the structures and properties of metal complexes, especially clusters. We hope that this Account will stimulate more efforts in exploiting new role of anions in various metal cluster systems. Anions can do much more than counterions for charge balance, and they should be considered in the design and synthesis of cluster-based functional materials.