Key Laboratory of Colloid and Interface Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, State Key Laboratory of Crystal Materials, Shandong University, Ji'nan, 250100, P. R. China.
Shandong Provincial Key Laboratory of Chemical Energy Storage and Novel Cell Technology, and School of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng, 252000, P. R. China.
Small. 2022 Feb;18(5):e2104524. doi: 10.1002/smll.202104524. Epub 2021 Nov 23.
Structural modulation of core-shell silver nanoclusters from the inside is a huge challenge but of great importance in their syntheses. Herein, two silver nanoclusters [Ag S @Ag ] (SD/Ag45b) and [Ag S @Ag ] (SD/Ag51a) are isolated in the presence of different kinds of sulfonic acids. Uniquely, SD/Ag45b and SD/Ag51a show typical core-shell structures with the similar Ag shell but different cores. The outer shell of 42 silver atoms comprises two Ag trigons at two poles encircled by three equatorial distorted square cupolas (J , Ag ). The core in SD/Ag45b is a silver trigon ligated by nine S ions (Ag S ), while a tricapped triangular prismatic Ag also ligated by the same amount of S ions (Ag S ) is observed in the inner core of SD/Ag51a. The electrospray ionization mass spectrometry (ESI-MS) indicates that the introduction of p-toluenesulfonic acid can realize the transformation from SD/Ag45b to Ag . SD/Ag45b and SD/Ag51a show inverse luminescence thermochromic behaviors in the near-infrared (NIR) region, mainly dictated by the inner silver cores. This work not only realizes the synthesis of new silver nanoclusters by core modulation but also provides a prototype to get molecular-level insight into the correlation between structure and luminescence thermochromism.
从内部对核壳型银纳米簇进行结构调制是一项巨大的挑战，但在其合成中非常重要。在此，在不同种类的磺酸存在下，分离得到了两种银纳米簇[Ag S @Ag ]（SD/Ag45b）和[Ag S @Ag ]（SD/Ag51a）。独特的是，SD/Ag45b 和 SD/Ag51a 具有典型的核壳结构，具有相似的 Ag 壳，但核不同。由 42 个银原子组成的外壳包含两个位于两极的 Ag 三角，被三个赤道扭曲的方形穹顶（J ，Ag ）包围。SD/Ag45b 的核是由九个 S 离子配位的银三角（Ag S ），而在 SD/Ag51a 的内核中观察到一个由相同数量的 S 离子配位的三角双锥 Ag （Ag S ）。电喷雾电离质谱（ESI-MS）表明，对甲苯磺酸的引入可以实现从 SD/Ag45b 到 Ag 的转化。SD/Ag45b 和 SD/Ag51a 在近红外（NIR）区域表现出相反的发光热致变色行为，主要由内部银核决定。这项工作不仅通过核调制实现了新的银纳米簇的合成，而且为深入了解结构与发光热致变色之间的关系提供了一个范例。
