Synthesis of Two Neutral Silver Alkynyl Nanoclusters by a Single Divalent Tetrahedral Anion Template and a Study of Their Optical Features
Lin‐Lin Hou, Fahime Bigdeli, Xun Cheng, Lingxiao Wang, Jingwen Zhang, Kuan‐Guan Liu, Ali Morsali
Abstract
The synthesis of nanoclusters from simple structural units is usually a challenging process because of the complexity and unpredictability of the self-assembly process of these types of compounds. Herein, two new neutral 19-nuclearity silver nanoclusters based on alkynyl ligands with the formulas [(CrO4)@Ag19(C≡CtBu)8(Ph2PO2)6(tfa)3(CH3OH)2] (1) and [(SO4)@Ag19(C≡CtBu)8(Ph2PO2)6(tfa)3(CH3OH)2] (2), in which tfa = trifluoroacetate, were synthesized, and their structures were investigated by single-crystal and powder X-ray diffraction, electrospray ionization mass spectrometry, elemental analyses, and Fourier transform infrared spectroscopy. The surface ligands of Ph2PO2H and trifluoroacetate were assembled through hydrogen bonding, metal–aromatic interactions, and coordination bonding around 19 silver atoms as the metal skeletons of the nanoclusters. Sulfate and chromate anions, as a template within the metal skeleton of clusters through bonding with silver atoms, stabilized the structure. In addition, the UV–vis absorption spectroscopy, luminescence properties, and thermal stability of the nanoclusters were investigated.