Benzoates-Induced High-Nuclearity Silver Thiolate Clusters

• Published in: Chemistry : a European journal 2018-01
• Main Authors: Su, Yanmin, Liu, Wei, Wang, Zhi, Wang, Shuao, Yu, Fei, Zhao, Quanqin, Wang, Xingpo, Tung, Chen-Ho, Sun, Di
• Format: Article
• Language: English
• ISSN: 1521-3765
• DOI: 10.1002/chem.201800007

Compared to the well-known anion-templated effects in shaping the silver-thiolate clusters, the influence from the organic ligands in the outer-shell is still poorly understood. Herein, we isolated and characterized three novel benzoate-functionalized high-nuclearity silver(I) thiolate clusters for the first time in the presence of diverse anion templates such as S2-, α-[Mo5O18]6-, and MoO42-. Single crystal X-ray analysis revealed that the nuclearities of three silver clusters (SD/Ag28-SD/Ag30) vary from 32, 38 to 78 with co-capped tBuS- and benzoate ligands on the surface. SD/Ag28 is a turtle-like cluster comprised of Ag29 shell caged an Ag3S3 trigon in the center, whereas SD/Ag29 is a prolate Ag38 sphere templated by α-[Mo5O18]6- anion. When changing benzoate to methoxyl substituted benzoate, we isolated SD/Ag30 as a very complicated core-shell spherical cluster comprised of an Ag57 shell and a vase-like Ag21S13 core. Four MoO42- anions are arranged into a supertetrahedron and located in the interstice between the core and shell. Introducing the bulky benzoate elaborately changes the nuclearity and arrangements of silver polygons on the shell of silver clusters, which is exemplified by comparing SD/Ag28 and a known similar silver thiolate cluster. Three new clusters emit luminescence in near infrared (NIR) region and show different thermochromic luminescence properties.