Homoleptic Platinum/Silver Superatoms Protected by Dithiolates: Linear Assemblies of Two and Three Centered Icosahedra Isolobal to Ne₂ and I₃^–

Abstract

Three bimetallic platinum/silver nanoclusters, PtAg 20 (dtp) 12 (1), Pt 2 Ag 33 (dtp) 17 (2), and Pt 3 Ag 44 (dtp) 22 (3) (dtp: dipropyl dithiophosphate), with cluster electron counts of 8, 16, and 22, respectively, were produced via a one-phase coreduction method. Singlecrystal X-ray structures reveal that their inner cores can be visualized as consisting of one, two, and three centered icosahedral Pt@Ag 12 units, respectively. In 2 and 3, these units are vertex-sharing and are assembled linearly. Intriguingly, the 22-electron alloy (3) is isolobal to the linear triiodide anion, I 3 − , and represents the first example of a cluster made of three superatoms whose bonding characteristics are similar to those of a triatomic molecular species.

Ligand-protected gold/silver superatoms: current status and emerging trends

“…87,[100][101][102][103][104][105] Bimetallic superatomic molecules Pt 2 Ag 33 (16e) and Pt 3 Ag 44 (22e) composed of icosahedral PtAg 12 (8e): their bonding schemes are analogues to those of dimers of rare gas atoms and trihalogen anions, respectively. 106 The Au 22 (22e) core in [Au 22 (Ph 2 P(CH 2 ) 8 PPh 2 ) 6 ] 0 corresponds to a homodimer of Au 11 (11e) 107 which are bonded by a 1D≡1D triple bond, similarly to transition metal binuclear complexes. 108 These examples imply that a class of quasi-molecules can be developed by bonding various superatomic units through various bonding schemes.…”

Atomically Precise Alloy Nanoclusters

“…[Ag Pt(dtp) 12 ] 0 (Figure 31 A) was synthesized when dipropyl dithiophosphate (dtp;S cheme 1D(2)) was used as al igand. [182] [Ag 33 Pt 2 (dtp) 17 ] 0 (Figure 31 B) (Figure 31 C) have also been synthesized in the same work. [182] [ 22 ] 0 .T he absorptione dge red shiftedw ith the number of connections in one dimension.…”

“…[182] [Ag 33 Pt 2 (dtp) 17 ] 0 (Figure 31 B) (Figure 31 C) have also been synthesized in the same work. [182] [ 22 ] 0 .T he absorptione dge red shiftedw ith the number of connections in one dimension. This behavior is in good agreement with that observed for the connection of the Au 13 core in one dimension.…”

“…[183,184] It wasf ound that the maximum PL wavelength was red shifted by the formation of such ac onnected structure (Figure 32 B). [182] . [181] (B) Experimental optical absorptionspectrum of [Ag 4 Pd 2 (2,4-SPhMe 2 ) 8 ] 0 together with the calculated spectrumf or [Ag 4 Pd 2 (SR) 8 ] 0 .…”

“…[Ag 20 Pt(dtp) 12 ] 0 (Figure 31 A) was synthesized when dipropyl dithiophosphate (dtp; Scheme 1 D(2)) was used as a ligand [182] . [Ag 33 Pt 2 (dtp) 17 ] 0 (Figure 31 B) and [Ag 44 Pt 3 (dtp) 22 ] 0 (Figure 31 C) have also been synthesized in the same work [182] . [Ag 20 Pt(dtp) 12 ] 0 , [Ag 33 Pt 2 (dtp) 17 ] 0 , and [Ag 44 Pt 3 (dtp) 22 ] 0 contain one, two, and three icosahedral Ag 12 Pt cores, respectively, with Pt located at the center of the Ag 12 Pt core.…”