Synthesis and Optical Properties of Unique Pt₁Ag₂₄ Nanoclusters with Mixed Exterior Motif Structures

Abstract

The atomic arrangement of metal nanoclusters plays a significant role in the structure–property correlation. Herein, we present a novel Pt1Ag24(SR)16­(PPh3)3 nanocluster with a unique structure, different from two reported Pt1Ag24 nanoclusters. The nanocluster was prepared via one-pot synthesis and solvent extraction. It has a centered icosahedral Pt1Ag12 kernel and an open shell composed of three Ag2(SR)3(PPh3) staple motifs and a unique trefoil-like Ag6(SR)7 motif. The three kinds of Pt1Ag24 nanoclusters have the same kernel but different shell configurations. The fine-tuning of structures is necessary and significant for the investigation of the relationship of structures and properties. The different UV–vis absorption spectra indicate that the optical properties of three Pt1Ag24 nanoclusters mainly depend on the exterior shell configuration and the metal–ligand interface. This work provides insights toward growth mechanism and the structure–property correlation of metal nanoclusters.

[Pt1Ag37(SAdm)21(Dppp)3Cl6]2+: intercluster transformation and photochemical properties

“…The free electron count of Pt 1 Ag 37 was calculated as 8 e ( i.e. , 37 (Ag)-21 (SR)-6 (Cl)-2 (charge) = 8 e ), the same as that of the reported Pt 1 Ag 24 (SR) 16 (PPh 3 ) 3 , 42 Pt 1 Ag 26 (2-EBT) 18 (PPh 3 ) 6 , 18 and Pt 1 Ag 28 (SAdm) 18 (PPh 3 ) 4 43 nanoclusters. The X-ray photoelectron spectroscopy (XPS) result revealed the presence of Pt, Ag, P, Cl, C and S in the nanocluster (Fig.…”

“…8,37–39 With respect to silver-rich alloy nanoclusters, especially, for doping Pt heteroatoms into Ag nanoclusters that gives rise to Pt@Ag alloy nanoclusters, several research efforts have been made for investigating the structure–property correlations at the atomic level. Despite this, a limited number of Pt doping sliver-rich nanoclusters were reported, including Pt 1 Ag 24 (SPhMe 2 ) 18 40 protected by thiolates, Pt 1 Ag 14 (SR) 6 (PPh 3 ) 8 , 41 Pt 1 Ag 24 (SR) 16 (PPh 3 ) 3 , 42 Pt 1 Ag 26 (2-EBT) 18 (PPh 3 ) 6 , 18 Pt 1 Ag 28 (S-Adm) 18 (PPh 3 ) 4 (Pt 1 Ag 28 for short), 43 Pt 1 Ag 31 (SR) 16 (DPPM) 3 Cl 3 44 coprotected by thiolates and phosphine ligands, Pt 5 Ag 22 (CCPh) 32 , 45 Pt 1 Ag 42 (CCPhMe) 28 , 46 stabilized by alkynyl, and so on. Among these nanoclusters, much effort has been devoted to the one-pot synthesis, such as Pt 1 Ag 24 (SPhMe 2 ) 18 , Pt 1 Ag 24 (SR) 16 (PPh 3 ) 3 , Pt 1 Ag 26 (2-EBT) 18 (PPh 3 ) 6 , Pt 5 Ag 22 (CCPh) 32 , and Pt 1 Ag 42 (CCPhMe) 28 .…”

“…Pt 1 Ag 24 (SR)16 (PPh 3 ) 3 ,42 Pt 1 Ag 26 (2-EBT) 18 (PPh 3 ) 6 ,18 Pt 1 Ag 28 (S-Adm) 18 (PPh 3 ) 4 (Pt 1 Ag 28 for short),43 Pt EBT) 18 (PPh 3 ) 6 , Pt 5 Ag 22 (CuCPh) 32 , and Pt 1 Ag 42 (CuCPhMe)28 . Meanwhile, the ligand exchange strategy is a versatile approach to achieve Pt@Ag alloy nanoclusters with novel structures and distinct properties.…”

Characterization of Pt-doping effects on nanoparticle emission: a theoretical look at Au24Pt(SH)18 and Au24Pt(SC3H7)18

“…In the literature, the energy of the main peak for Au 24 Pt(SR) 18 clusters has ranged from 2.07-2.12 eV, [33][34][35]64 with two other optical features of note: one broad band in the IR range, and one high energy shoulder on the edge of the UV spectrum. These three spectral features are similar to those seen in [Au 25 (SR) 18 ] q clusters (q ¼ À1, 0, +1), where the anionic cluster has a high energy shoulder around 403 nm (3.08 eV), a peak at 450 nm (2.76 eV) and a broad peak around 680 nm (1.81 eV).…”