A chloride-doped silver-sulfide cluster [Ag148S26Cl30(CCBut)60]6+: hierarchical assembly, enhanced luminescence and cytotoxicity to cancer cells.

The formation of high-nuclear silver(I) clusters remains elusive and their potential applications are still underdeveloped. Herein, we report an unprecedented gigantic Ag148 ([Ag148S26Cl30(CCBut)60](SbF6)6) cluster co-templated by Cl- and S2-, which was well-defined by single-crystal X-ray diffraction and high-resolution mass spectrometry. The cluster exhibits a hierarchical structure consisting of fused Ag24X16 kernel, Ag60X20 shell and "cluster of clusters assembling" of four pentagonal concave polyhedral {Ag16X5} units. Furthermore, the silver cluster emits red light at room temperature with a prominent 39.6% QY. The cellular uptake and cytotoxicity indicate that Ag148 induces apoptosis of cancer cells in a dose-dependent manner.