Precise Implantation of an Archimedean Ag@Cu₁₂ Cuboctahedron into a Platonic Cu₄Bis(diphenylphosphino)hexane₆ Tetrahedron

Abstract

Precision loading of nanoclusters in confined spaces, which has been enthusiastically pursued in the scientific realm, is still associated with some mysteries of “how”, “when”, and “why”. Here, we isolated two similar heterometallic cluster-in-cage compounds, [Ag@Cu12S8@Cu4(dpph)6]­X (X = OH, SD/AgCu16a and X = PF6, SD/AgCu16b; SD = SunDi), by use of an antigalvanic reaction between organometallic [PhCCCu] n and Ph3CSH with elemental silver. Both compounds are formed by fitting an Archimedean Ag@Cu12 cuboctahedral cluster into a Platonic Cu4(dpph)6 tetrahedral cage [dpph = bis­(diphenylphosphino)­hexane]. The Ag@Cu12 cluster is a hollow cuboctahedral Cu12 cage filled with a central AgI atom, and all eight triangular faces of the Ag@Cu12 cuboctahedron are triply capped by eight S2– ions, four of which in a tetrahedral array further internally pillar four Cu vertices of the outer Cu4(dpph)6 tetrahedron, fixing the cluster in the cage. Both compounds can be deemed as molecular fragments excised from porous nanomaterials filled with discrete nanoclusters, thus providing more details for understanding the confined growth of atomically precise nanoclusters. Electrospray ionization mass spectrometry (ESI-MS) reveals that the AgCu16 cluster is quite stable in CH2Cl2 and can stepwise lose dpph ligand in the gas phase under increased collision energy. This work not only presents a precise aggregation of metal atoms in a confined cavity to form a cluster-in-cage compound but also provides deep insights into the binding and geometry matching between clusters and cages in one entity.

Cu Doping‐Induced Transformation from [Ag62S12(SBut)32]2+ to [Ag62−xCuxS12(SBut)32]4+ Nanocluster

“…The results of ESI-MS revealed that the product of this alloy is a mixture nanocluster with different number of Cu atoms (10 ~21) doping. Similarly, the mixed doping of copper atom into silver nanolcuster was also reported for AgCu 16 nanocluster in the recent studies of Han et al [33] As shown in Figure S2, TGA reveals a weight loss of 42.96%, which is very close to the theoretical value (43.16%) for [Ag 45 Cu 17 S 12 (SC 4 H 9 ) 32 ](BPh 4 ) 4 . XPS measurements were carried out to reveal the element type and compared the binding energies of Ag in Ag 62À x Cu x and Ag 62 .…”

Acid–base resistant ligand-modified molybdenum–sulfur clusters with enhanced photocatalytic activity towards hydrogen evolution

“…There were also no other fragment peaks detected under in-source energy-dependent mass spectra between 0 and 100 eV, further indicating the excellent stability of MoS-MBTZ. 49,50 As the voltage of the ion source was increased, the intensity of the fragment peaks attributed to the dimers gradually decreased and eventually disappeared as the weak interaction between the clusters in a dimer is overcome (Fig. 2d).…”

[Cu18H3(S-Adm)12(PPh3)4Cl2]: fusion of Platonic and Johnson solids through a Cu(0) center and its photophysical properties

“…Due to the quantum connement effect, the discrete energy level of the NC offers unprecedented opportunities to nd optoelectronic applicability. 24,68,69 DFT calculations were employed to scrutinize the electronic structure of the Cu 18 NC. The projected density of states (PDOS) analysis reveals that the valence band region of this NC is predominantly occupied by Cu(d) states (Fig.…”