Silver Clusters Coprotected by Different Diphosphine and Thiol Ligands
Yu-Han Xia, Jun-Jie Fang, Xin-Yan Xia, Zheng Liu, Yun-Peng Xie*, and Xing Lu
Cryst. Growth Des. 2022. https://doi.org/10.1021/acs.cgd.2c00744
Abstract：The diphosphine ligands can act as auxiliary ligands for the thiol ligands to generate novel silver clusters. Here, we report five silver thiolated clusters protected by diphosphine ligands, namely, [Ag11(iPrS)9(dppm)3](BPh4)2 (1, dppm = bis(diphenylphosphino)methane), S@Ag26(iPrS)16(CF3COO)8(dpph)2·3DMF (2, dpph = 1,6-bis(diphenylphosphino)hexane), S@Ag26(iPrS)16(CF3COO)8(dpppe)2·2DMF (3, dpppe = 1,5-bis(diphenylphosphino)pentane), AgS2@Ag24(tBuS)18(dpppe)2(BF4)3 (4), and [SO4@Ag20(iPrS)10(CF3COO)8(dpphS2)2]n (5, dpphS2 = 1,6-bis(diphenylphosphino)hexane disulfide). Their structures were characterized by single-crystal X-ray diffraction, which revealed that 1 presents a triangular structure covered by three diphosphine ligands, and there are strong C–H···π interactions between clusters and between clusters and counterions. Clusters 2 and 3 are olive-shaped structures, and cluster 4 is a box-type structure. Clusters 2–4 all have two diphosphine ligands at both ends. Cluster 5 is a chainlike structure connected by dpphS2. Among them, cluster 1 exhibits photoluminescence (PL) properties, and the emission of its solution phase is red-shifted compared to the crystalline state.
摘要：双膦配体可作为硫醇配体的辅助配体以产生新颖的银簇，在这项工作中，我们报道了5种由双齿膦配体保护的硫醇化银簇，即[Ag11(iPrS)9(dppm)3](BPh4)2 (1)，Ag26S(iPrS)16(CF3COO)8(dpph)2·3DMF (2)，Ag26S(iPrS)16(CF3COO)8(dpppe)2·2DMF (3)，S2@Ag25(tBuS)18(dpppe)2(BF4)3 (4)和[Ag20S4(iPrS)10(CF3COO)6(dpph)2]n (5)。通过单晶X射线衍射表征了其结构，表明1为由三个双齿膦配体覆盖的三角形结构，且簇之间以及簇与抗衡离子具有强的C-H···π相互作用。2和3均为橄榄形结构，4为箱型结构。2-4的两端都有两个双齿膦配体。5是由dpphS2连接的一维链状结构。其中，1表现良好的荧光性质，与结晶态的发射相比，溶液相的发射红移。
