A route to metalloligands consolidated silver nanoclusters by grafting thiacalix[4]arene onto polyoxovanadates

Metalloligands provide a potent strategy for manipulating the surface metal arrangements of metal nanoclusters, but their synthesis and subsequent installation onto metal nanoclusters remains a significant challenge. Herein, two atomically precise silver nanoclusters {Ag(14)[(TC4A)(6)(V(9)O(16))](CyS)(3)} (Ag14) and {Ag(43)S[(TC4A)(2)(V(4)O(9))](3)(CyS)(9)(PhCOO)(3)Cl(3)(SO(4))(4)(DMF)(3)·6DMF} (Ag43) are synthesized by controlling reaction temperature (H(4)TC4A = p-tert-butylthiacalix[4]arene). Interestingly, the 3D scaffold-like [(TC4A)(6)(V(9)O(16))](11-) metalloligand in Ag14 and 1D arcuate [(TC4A)(2)(V(4)O(9))](6)(-) metalloligand in Ag43 exhibit a dual role that is the internal polyoxovanadates as anion template and the surface TC4A(4-) as the passivating agent. Furthermore, the thermal-induced structure transformation between Ag14 and Ag43 is achieved based on the temperature-dependent assembly process. Ag14 shows superior photothermal conversion performance than Ag43 in solid state indicating its potential for remote laser ignition. Here, we show the potential of two thiacalix[4]arene modified polyoxovanadates metalloligands in the assembly of metal nanoclusters and provide a cornerstone for the remote laser ignition applications of silver nanoclusters.