[Cu₂₃(PhSe)₁₆(Ph₃P)₈(H)₆]·BF₄: Atomic-Level Insights into Cuboidal Polyhydrido Copper Nanoclusters and Their Quasi-simple Cubic Self-Assembly

Abstract

Polyhydrido copper nanoclusters are an emerging class of nanomaterials. Unfortunately, insights into the structural evolution and structure-property relationship of such copper nanoclusters are scant, due to the difficulty of synthesizing and crystallizing nanoclusters with high nuclearity and new morphologies. Here, we report an anisotropic cuboidal polyhydrido copper nanocluster, [Cu23(PhSe)16(Ph3P)8(H)6]‧BF4, with a distorted cuboctahedral Cu13 core stabilized by two square protecting motifs and six hydrides. The cuboidal nanoclusters self-assemble into a quasi-simple cubic packing pattern with perfect face-to-face contact of neighboring nanoclusters and interdigitation of intercluster surface ligands. Atomic-level observations reveal the crucial role that subtle synergies between nanocluster geometry and intercluster noncovalent interactions play in guiding nanocluster self-assembly. In addition, a comparison with previously reported analogous metal nanoclusters points to bulky monodentate phosphine ligands as a potent inducing agent for the formation of rectangular hexahedral nanoclusters. These findings have significant implications for the controllable synthesis of polyhedral nanomaterials and their superstructures.

[Cu36H10(PET)24(PPh3)6Cl2] Reveals Surface Vacancy Defects in Ligand-Stabilized Metal Nanoclusters

“…In addition, the stability of Cu36 was also evaluated by monitoring its UV–vis absorption spectrum in solution at room temperature. As shown in Figure S17, Cu36 is found to be stable in chloroform for at least 24 h, and its stability is comparable to that of other reported copper nanoclusters …”

“…NaBH 4 is the most common reductant for the synthesis of metal nanoparticles and nanoclusters. Both PETH and PPh 3 have been widely used as the protective ligands in the synthesis of metal nanoclusters. − PETH usually acts as the primary ligand with diverse coordination modes to metal atoms, thus stabilizing the framework of the nanocluster. On the other hand, PPh 3 with its relatively rigid and bulky structure is used as an auxiliary ligand, which is conducive to the crystallization of nanoclusters.…”

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

“…38,39 Such types of core geometry and the growth of the core via kernel fusion through vertex sharing are observed among the thiolated Cu nanoclusters for the rst time, and are vividly distinct from other common cores, i.e., icosahedron or cuboctahedron cores. 11,21,[40][41][42] The attachment of the Platonic and Johnson solid is stabilized by two m 3 -bridged hydrides (Fig. 2b and S2 †).…”

“…, icosahedron or cuboctahedron cores. 11,21,40–42 The attachment of the Platonic and Johnson solid is stabilized by two μ 3 -bridged hydrides (Fig. 2b and S2†).…”

[Au16Ag43H12(SPhCl2)34]5–: An Au–Ag Alloy Nanocluster with 12 Hydrides and Its Enlightenment on Nanocluster Structural Evolution

“…Such a tendency is rationalized from two aspects: (i) the ultrasmall size of the H – and (ii) the analogy between the d 10 metal (mainly Au, Ag, and Cu) and H owing to their similar electron configurations―a metal atom at a low-coordination site of a cluster can be substituted by an introduced H atom while retaining its geometric and electronic structures. , Since the isolation of the hexameric [CuH­(PPh 3 )] 6 , several efforts have been made for extending the research scope of metal hydride clusters. Especially in this half a decade, the research of metal hydride nanoclusters has been expanded from copper to gold and silver clusters. − However, the hydride ligands are rarely observed in alloy nanoclusters, especially in high-nuclearity alloy nanoclusters, and such a deficiency impedes a fully understating of hydride···metal interactions in nanocluster science. The subject of alloy hydride nanoclusters calls for more effort.…”