Encapsulating Hydrides and Main-Group Anions in d10-Metal Clusters Stabilized by 1,1-Dichalcogeno Ligands
Encapsulating Hydrides and Main-Group Anions in d10-Metal Clusters Stabilized by 1,1-Dichalcogeno Ligands
复制标题
DOI：
10.1007/s10876-013-0671-3
复制
发表时间：
2014-04
影响因子：
2.8
通讯作者：
C. Latouche;C. W. Liu;J. Saillard
中科院分区：
文献类型：
--
作者：
C. Latouche;C. W. Liu;J. Saillard
Cu(I)和Ag(I)可以与1,1-二硫代（硒）配体形成各种类型的簇，其框架由桥接配体提供的金属-硫键维持。金属中心通常是三配位的，因此具有s价和/或p价的接受轨道。没有正式的金属-金属成键，只有弱的d10 - d10相互作用，有利于金属接受轨道之间的重叠。它们的成键组合通常适合于与被封装阴离子的已占价轨道相互作用。因此，许多这些簇能够封装阴离子，这种情况往往通过建立重要的主-客体键来稳定整个结构。阴离子的包封作用不仅可以稳定簇笼，还可以显著地改变簇笼的结构，或者作为一个模板来稳定那些不会以空簇存在的物种。本文综述了所有已知的以1,1-二硫代配体修饰并含有原子阴离子的d10金属簇的合成、结构和成键。它们的结构根据大小和形状进行了分析。讨论了其中一些材料的光致发光特性。
Cu(I) and Ag(I) can form with 1,1-dithio(seleno) ligands various types of clusters, the framework of which being maintained by the metal–chalcogen bonds provided by the bridging ligands. The metal centers are generally tricoordinated and consequently possess an accepting orbital of valence s and/or p character. There is no formal metal–metal bonding, but only weak d10–d10interactions which favor the overlap between the metal accepting orbitals. Their bonding combinations are generally suited for interacting with the occupied valence orbitals of an encapsulated anion. Thus, many of these clusters are able to encapsulate anions, a situation which tends to stabilize the whole structure through building of significant host–guest bonding. Not only is the anion encapsulation effect to stabilize the cluster cage, but it can also significantly modify its structure, or act as a template in the stabilization of species which would not exist as empty clusters. This paper reviews the synthesis, structure and bonding of all the known clusters of d10metals decorated with 1,1-dichalchogeno ligands and containing entrapped atomic anions. Their structures are analyzed with respect to size and shape. The photoluminescence properties of some of them are discussed.