Parasitism in Metal Nanoclusters: A Case Study of (AuAg)₂₅·(AuAg)₂₇

Studying the interactions of atomically precise metal nanoclusters in their assembly systems is of great significance in the nanomaterial research field, which has attracted increasing interest in the last few decades. Herein, we report the cocrystallization of two oppositely charged atomically precise metal nanoclusters in one unit cell: [Au1Ag24(SR)18]– ((AuAg)25 for short) and [AuxAg27–x(Dppf)4(SR)9]2+ (x = 10–12; (AuAg)27 for short) with a 1:1 ratio. (AuAg)27 could maintain its structure in the presence of (AuAg)25, whether in the crystalline and the solution state, while the metastable (AuAg)27 component underwent a spontaneous transformation to (AuAg)16(Dppf)2(SR)8 after dissociating the (AuAg)25 component from this cocrystal, demonstrating the “parasitism” relationship of the (AuAg)27 component over (AuAg)25 in this dual-cluster system. This work enriches the family of cluster-based assemblies and elucidates the delicate relationship between nanoparticles of cocrystals

Parasitism in Metal Nanoclusters: A Case Study of (AuAg)₂₅·(AuAg)₂₇

Studying the interactions of atomically precise metal nanoclusters in their assembly systems is of great significance in the nanomaterial research field, which has attracted increasing interest in the last few decades. Herein, we report the cocrystallization of two oppositely charged atomically precise metal nanoclusters in one unit cell: [Au1Ag24(SR)18]– ((AuAg)25 for short) and [AuxAg27–x(Dppf)4(SR)9]2+ (x = 10–12; (AuAg)27 for short) with a 1:1 ratio. (AuAg)27 could maintain its structure in the presence of (AuAg)25, whether in the crystalline and the solution state, while the metastable (AuAg)27 component underwent a spontaneous transformation to (AuAg)16(Dppf)2(SR)8 after dissociating the (AuAg)25 component from this cocrystal, demonstrating the “parasitism” relationship of the (AuAg)27 component over (AuAg)25 in this dual-cluster system. This work enriches the family of cluster-based assemblies and elucidates the delicate relationship between nanoparticles of cocrystals

Parasitism in Metal Nanoclusters: A Case Study of (AuAg)₂₅·(AuAg)₂₇

Studying the interactions of atomically precise metal nanoclusters in their assembly systems is of great significance in the nanomaterial research field, which has attracted increasing interest in the last few decades. Herein, we report the cocrystallization of two oppositely charged atomically precise metal nanoclusters in one unit cell: [Au1Ag24(SR)18]– ((AuAg)25 for short) and [AuxAg27–x(Dppf)4(SR)9]2+ (x = 10–12; (AuAg)27 for short) with a 1:1 ratio. (AuAg)27 could maintain its structure in the presence of (AuAg)25, whether in the crystalline and the solution state, while the metastable (AuAg)27 component underwent a spontaneous transformation to (AuAg)16(Dppf)2(SR)8 after dissociating the (AuAg)25 component from this cocrystal, demonstrating the “parasitism” relationship of the (AuAg)27 component over (AuAg)25 in this dual-cluster system. This work enriches the family of cluster-based assemblies and elucidates the delicate relationship between nanoparticles of cocrystals

Structure Determination of the Cl-Enriched [Ag₅₂(SAdm)₃₁Cl₁₃]²⁺ Nanocluster

Cl atoms can serve as the innermost core, the peripheral ligand, or the counterions of metal nanoclusters. Herein, we report the structural determination a Cl-enriched [Ag52(SAdm)31Cl13]2+. The ratio of Cl to AdmSH is quite high compared to those of other nanoclusters. Structurally, nine Cl atoms, existing at the interlayer of the inner kernel and the surface motif, serve as the bridging ligands to sustain the robustness of the whole structure. Interestingly, four Cl atoms on the motif structure can be substituted by Br. This work allows us to clear the regulation of Cl ligands in the structural construction of metal nanoclusters

Doping Copper Atoms into the Nanocluster Kernel: Total Structure Determination of [Cu₃₀Ag₆₁(SAdm)₃₈S₃](BPh₄)

Doping active metal (i.e., Cu) into the kernel of noble metal nanoclusters (i.e., Au/Ag nanocluster) remains challenging in the synthesis of alloy nanoclusters. Herein, we report the synthesis and the total structure determination of a bimetallic [Ag61Cu30(SAdm)38S3]­BPh4 (Ag61Cu30) nanocluster. The Ag61Cu30 nanocluster is composed of an Ag13@Cu30 kernel which is further capped by a peripheral Ag48(SAdm)38S3 shell. The icosidodecahedron Cu30 middle layer connects the innermost icosahedral Ag13 core and Ag atoms at the outermost Ag48(SR)38S3 shell, demonstrating that the Cu atoms in the Cu30 layer are in a metallic state

Ag₅₀(Dppm)₆(SR)₃₀ and Its Homologue Au_<i>x</i>Ag_{50–<i>x</i>}(Dppm)₆(SR)₃₀ Alloy Nanocluster: Seeded Growth, Structure Determination, and Differences in Properties

A large thiolate/phosphine coprotected Ag₅₀(Dppm)₆(SR)₃₀ nanocluster was synthesized through the further growth of Ag₄₄(SR)₃₀ nanocluster and characterized by X-ray photoelectron spectroscopy (XPS), electrospray ionization mass spectrometry (ESI-MS), and single-crystal X-ray analysis. This new nanocluster comprised a 32-metal-atom dodecahedral kernel and two symmetrical Ag₉(SR)₁₅P₆ ring motifs. The 20 valence electrons correspond to shell closure in the Jellium model. Moreover, this nanocluster could be alloyed by templated/galvanic metal exchange to the homologue Au_<i>x</i>Ag_{50–<i>x</i>}(Dppm)₆(SR)₃₀ nanocluster; the latter showed much higher thermal stability than the Ag₅₀(Dppm)₆(SR)₃₀ nanocluster. Further experiments were conducted to study the optical, electrical, and photoluminescence properties of both nanoclusters. Our work not only reports two new larger size nanoclusters but also reveals a new way to synthesize larger size silver and alloy nanoclusters, that is, controlled growth/alloying

Ag₅₀(Dppm)₆(SR)₃₀ and Its Homologue Au_<i>x</i>Ag_{50–<i>x</i>}(Dppm)₆(SR)₃₀ Alloy Nanocluster: Seeded Growth, Structure Determination, and Differences in Properties

A large thiolate/phosphine coprotected Ag50(Dppm)6(SR)30 nanocluster was synthesized through the further growth of Ag44(SR)30 nanocluster and characterized by X-ray photoelectron spectroscopy (XPS), electrospray ionization mass spectrometry (ESI-MS), and single-crystal X-ray analysis. This new nanocluster comprised a 32-metal-atom dodecahedral kernel and two symmetrical Ag9(SR)15P6 ring motifs. The 20 valence electrons correspond to shell closure in the Jellium model. Moreover, this nanocluster could be alloyed by templated/galvanic metal exchange to the homologue AuxAg50–x(Dppm)6(SR)30 nanocluster; the latter showed much higher thermal stability than the Ag50(Dppm)6(SR)30 nanocluster. Further experiments were conducted to study the optical, electrical, and photoluminescence properties of both nanoclusters. Our work not only reports two new larger size nanoclusters but also reveals a new way to synthesize larger size silver and alloy nanoclusters, that is, controlled growth/alloying

Ag₅₀(Dppm)₆(SR)₃₀ and Its Homologue Au_<i>x</i>Ag_{50–<i>x</i>}(Dppm)₆(SR)₃₀ Alloy Nanocluster: Seeded Growth, Structure Determination, and Differences in Properties

A large thiolate/phosphine coprotected Ag₅₀(Dppm)₆(SR)₃₀ nanocluster was synthesized through the further growth of Ag₄₄(SR)₃₀ nanocluster and characterized by X-ray photoelectron spectroscopy (XPS), electrospray ionization mass spectrometry (ESI-MS), and single-crystal X-ray analysis. This new nanocluster comprised a 32-metal-atom dodecahedral kernel and two symmetrical Ag₉(SR)₁₅P₆ ring motifs. The 20 valence electrons correspond to shell closure in the Jellium model. Moreover, this nanocluster could be alloyed by templated/galvanic metal exchange to the homologue Au_<i>x</i>Ag_{50–<i>x</i>}(Dppm)₆(SR)₃₀ nanocluster; the latter showed much higher thermal stability than the Ag₅₀(Dppm)₆(SR)₃₀ nanocluster. Further experiments were conducted to study the optical, electrical, and photoluminescence properties of both nanoclusters. Our work not only reports two new larger size nanoclusters but also reveals a new way to synthesize larger size silver and alloy nanoclusters, that is, controlled growth/alloying