Luo Geng-Geng, Su Hai-Feng, Xiao An, Wang Zhi, Zhao Yang, Wu Qiao-Yu, Wu Ji-Huai, Sun Di, Zheng Lan-Sun
Key Laboratory of Environmental Friendly Function Materials, Ministry of Education, College of Materials Science and Engineering, Huaqiao University, Xiamen, 361021, P.R. China.
State Key Laboratory for Physical Chemistry of Solid Surface and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, P.R. China.
Chemistry. 2017 Oct 17;23(58):14420-14424. doi: 10.1002/chem.201703468. Epub 2017 Sep 22.
The synthesis of Group 11 metal chalcogenide supertetrahedral clusters (SCs) still remains a great challenge mainly due to the high tendency of metal aggregation through metallophilicity and global charge balance. Demonstrated herein are the preparation, crystallographic characterization, and optical properties of two stable silver-sulfur SCs through ligand-control; one as a discrete zero-dimensional (0D) V3,4-type cluster and the other as a one-dimensional (1D) zigzag chain extended by alternating V3,2-type clusters. The notation Vn,m (where n is the number of metal layers, and m is the number of vacant corners) is used to describe a new series of vacant-corner SCs, which can be derived from the regular Tn clusters. The existence of vacant-corner-type SCs may be ascribed to the low valence and tri-coordinated environment of silver ions. These are the first representatives of structurally determined silver-sulfur tetrahedral clusters thus far. This work enriches the coinage-metal chalcogenide tetrahedral cluster portfolio, discovers vacant-corner SCs present in silver-sulfur hybrid tetrahedral clusters, and provides effective means for further development of Group 11 coinage-metal chalcogenide SCs.
第11族金属硫族化物超四面体簇（SCs）的合成仍然是一个巨大的挑战，主要是因为通过亲金属性和整体电荷平衡，金属聚集的倾向很高。本文展示了通过配体控制制备的两种稳定的银硫SCs的制备、晶体学表征和光学性质；一种是离散的零维（0D）V3,4型簇，另一种是由交替的V3,2型簇延伸而成的一维（1D）之字形链。符号Vn,m（其中n是金属层数，m是空角数）用于描述一系列新的空角SCs，它们可以从规则的Tn簇衍生而来。空角型SCs的存在可能归因于银离子的低价态和三配位环境。这些是迄今为止结构确定的银硫四面体簇的首批代表。这项工作丰富了贵金属硫族化物四面体簇的组合，发现了银硫混合四面体簇中存在的空角SCs，并为进一步开发第11族贵金属硫族化物SCs提供了有效手段。
