Identification of an Eight-Electron Superatomic Cluster and Its Alloy in One Co-crystal Structure

Abstract

Herein we report a crystal structure of [Au 0.5

Cl@Ag22Au6(4‐TBBT)28(PPh4): A Chloride‐Centered Ag−Au Bimetallic Cluster for Optics

“…Here, there is a chlorine atom present in the inner core of Ag 22 (i. e., Cl@Ag 22 SR 16 ), which could be driven by strong binding interaction of the chlorine and Ag atoms, and anchored by the prodigious bridging linkage of the RS−Au−SR staples [32] . The solvent used for the synthesis of Cl@Ag 22 Au 6 (4‐TBBT) 28 (PPh 4 ) is composed of the mixture of methanol and CH 2 Cl 2, It is therefore inferred that the central chloride atom is originated from the decomposition of the CH 2 Cl 2 used in the synthesis of the cluster, which is in agreement with the previous reported Cl@Ag 14 , [21e] Cl@Ag 19 , [21a] and Cl@Ag 8 [21b] clusters. The average Ag−S bond distance in the whole framework is 2.61 Å, similar to thiolate protected Ag 44 (2.60 Å); while the average Ag−Ag bond distances is 3.04 Å, shorter than the average Ag−Ag bond distance in Ag 44 (SR) 30 (3.23 Å) and Au 12 Ag 32 (SR) 30 (3.23 Å), [15] indicative of reinforced metal‐metal interactions in the Cl@Ag 22 SR 16 cluster.…”

Cocrystallization of Atomically Precise Nanoclusters

“…In addition, the cocrystallized nanoclusters should have very similar components in terms of both metal composition and ligand type, or the potential metal/ligand-exchange process might result in composition disorder of the cocrystallized system and the further inability to cocrystallize. Since 2018, when nanocluster cocrystallization between (AuAg) 45 and (AuAg) 267 was reported, several efforts have been made to develop more nanocluster cocrystallization cases and investigate cocrystallization-triggered property variations. − Of note, most of these reported cocrystallized nanoclusters were prepared through a one-pot synthetic method, which essentially prevented the metal/ligand exchange-induced disorder.…”

A New Synthetic Methodology in the Preparation of Bimetallic Chalcogenide Clusters via Cluster-to-Cluster Transformations

“…Hence, the crystal structure can be best represented as [Cu 3 Ag 7 (Se){Se 2 P(O i Pr) 2 } 8 ] 0.6 [Cu 4 Ag 6 (Se){Se 2 P(O i Pr) 2 } 8 ] 0.4 ([ 3a ] 0.6 [ 3b ] 0.4 ). It is worthwhile to mention that the phenomenon of co-crystallization is frequently observed in heterometallic clusters [ 26 , 27 , 28 , 29 , 30 , 31 ] especially for two heterometals occupying the same site. The copper atoms in M 10 (Se) are distributed in six positions, where two Cu are fully occupied at two brown ellipsoids ( Figure 1 g) and the rest Cu atoms are randomly disordered at four cyan ellipsoids (see Figure S1 ).…”