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.