Thermally Hypsochromic or Bathochromic Emissions? The Silver Nuclei Does Matter

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 [Ag3 S9 @Ag42 ] (SD/Ag45b) and [Ag9 S9 @Ag42 ] (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 Ag42 shell but different cores. The outer shell of 42 silver atoms comprises two Ag3 trigons at two poles encircled by three equatorial distorted square cupolas (J4 , Ag12 ). The core in SD/Ag45b is a silver trigon ligated by nine S2- ions (Ag3 S9 ), while a tricapped triangular prismatic Ag9 also ligated by the same amount of S2- ions (Ag9 S9 ) 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 Ag51 . 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.