Stepwise Assembly of Ag₄₂ Nanocalices Based on a Mo^VI-Anchored Thiacalix[4]arene Metalloligand.

Abstract

Metalloligand strategy has been well recognized in the syntheses of heterometallic coordination polymers; however, such a strategy used in the assembly of silver nanoclusters is not broadly available. Herein, we report the stepwise syntheses of a family of halogen-templated Ag₄₂ nanoclusters (<b>Ag42c</b>-<b>Ag42f</b>) based on Mo^VI-anchored <i>p</i>-<i>tert</i>-butylthiacalix[4]arene (H₄TC4A) as a metalloligand (hereafter named MoO₃-TC4A). X-ray crystallography demonstrates that they are similar <i>C</i>₃-symmetric silver-organic nanocalices capped by six MoO₃-TC4A metalloligands, which are evenly distributed up and down the base of 42 silver atoms. These nanoclusters can be disassembled to six bowl-shaped [Ag₁₁(MoO₃-TC4A)(RS)₃] secondary building units (SBUs, R = Et or ^<i>n</i>Pr), which are fused together in a face-sharing fashion surrounding Cl^- or Br^- as a central anion template. The electrospray mass spectrometry (ESI-MS) indicates their high stabilities in solution and verifies the formation of the MoO₃-TC4A metalloligand, thereby rationalizing the overall stepwise assembly process for them. Moreover, <b>Ag42c</b> shows lower cytotoxicity and better activity against the HepG-2 cell line than MCF-7 and BGC-823. These results not only exemplify the effectiveness of a thiacalix[4]arene-based metalloligand in the assembly of silver nanoclusters but also give us profound insight about the step-by-step assembly process in silver nanoclusters.