Wang Zhi, Zhu Yan-Jie, Han Bao-Liang, Li Yi-Zhi, Tung Chen-Ho, Sun Di
School of Chemistry and Chemical Engineering, State Key Laboratory of Crystal Materials, Shandong University, Ji'nan, 250100, People's Republic of China.
Nat Commun. 2023 Aug 31;14(1):5295. doi: 10.1038/s41467-023-41050-x.
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(TC4A)(VO)} (Ag14) and {AgS(TC4A)(VO)(PhCOO)Cl(SO)(DMF)·6DMF} (Ag43) are synthesized by controlling reaction temperature (HTC4A = p-tert-butylthiacalix[4]arene). Interestingly, the 3D scaffold-like [(TC4A)(VO)] metalloligand in Ag14 and 1D arcuate [(TC4A)(VO)] metalloligand in Ag43 exhibit a dual role that is the internal polyoxovanadates as anion template and the surface TC4A 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.
金属配体为调控金属纳米团簇的表面金属排列提供了一种有效的策略，但其合成以及随后在金属纳米团簇上的安装仍然是一项重大挑战。在此，通过控制反应温度合成了两个原子精确的银纳米团簇{Ag(TC4A)(VO)}（Ag14）和{AgS(TC4A)(VO)(PhCOO)Cl(SO)(DMF)·6DMF}（Ag43）（HTC4A = 对叔丁基硫杂杯[4]芳烃）。有趣的是，Ag14中的三维支架状[(TC4A)(VO)]金属配体和Ag43中的一维弧形[(TC4A)(VO)]金属配体具有双重作用，即内部的多钒酸盐作为阴离子模板，表面的TC4A作为钝化剂。此外，基于温度依赖的组装过程实现了Ag14和Ag43之间的热诱导结构转变。在固态下，Ag14比Ag43表现出更优异的光热转换性能，表明其在远程激光点火方面的潜力。在此，我们展示了两种硫杂杯[4]芳烃修饰的多钒酸盐金属配体在金属纳米团簇组装中的潜力，并为银纳米团簇的远程激光点火应用奠定了基础。
