Temperature‐Mediated Template Release: Facile Growth of Copper(I) Mixed Ethynediide/Isopropylethynide Nanoclusters

Abstract

In the comproportionation reaction of Cu X and Cu with isopropylacetylene (iPr-C≡C-H), the ethynediide species C is generated via concomitant C-H/C-C bond cleavage of the iPr-C≡C-H precursor under moderate temperature to direct the formation of Cu mixed ethynediide/isopropylethynide nanoclusters (potentially explosive). The active ethynediide dianion C exhibits chameleon-like templating behavior to form C @Cu (m=6 (3, 4), 7 (2, 4), 8 (1)) central structural units for successive formation of {C ⊂Cu } (1, 2), {6 C ⊂Cu } (3), and {18 C ⊂Cu } (4) complexes. Bearing the highest C content, complex 4 features an unprecedented nanoscale Cu C kernel. Furthermore, 1-3 exhibit structure-controlled photoluminescence in the solid state.

Ether‐Soluble Cu53 Nanoclusters as an Effective Precursor of High‐Quality CuI Films for Optoelectronic Applications

“…Unfortunately, compared to Ag and Au systems, the lower Cu I /Cu 0 half‐cell potential (0.52 V) makes Cu 0 ‐containing Cu nanoclusters highly air‐sensitive, often seriously hindering the synthesis of high‐nuclearity Cu I /Cu 0 clusters . The synthetic strategy of alkynyl‐protected Cu clusters can be grouped into two categories: 1) the reaction of Cu powder and Cu 2+ which prefers to achieve Cu I clusters, such as Cu 14 , Cu 15 , Cu 16 , Cu 17 , Cu 18 , Cu 24 , Cu 33 , Cu 48 , Cu 62 , Cu 92 ; and 2) the direct reduction of Cu + complexes, which is likely to generate Cu 0 ‐containing clusters, one notable example being Cu 20 . However, it remains challenging to develop a general method for the synthesis of stable high‐nuclearity Cu I /Cu 0 clusters.…”

“…After being stored at 4 °C, red block crystals (Supporting Information, Figure S2) were grown from the solution in 4 days. We believe that in the synthesis, Cu powder reduces Cu 2+ complexes through reverse disproportionation to yield intermediate Cu I cluster(s), which are subsequently reduced by Ph 2 SiH 2 to produce the Cu I /Cu 0 clusters . The cooperation of Cu powder and Ph 2 SiH 2 makes it more convenient to achieve high‐nuclearity Cu I /Cu 0 clusters.…”

Tertiary Hierarchical Complexity in Assemblies of Sulfur-Bridged Metal Chiral Clusters

“…In the Cu 4 caps, the Cu−Cu bond lengths from the apex to the three base Cu atoms are equally 2.737 Å, while the distance between the Cu atoms on all three edges in the triangular base are 3.606 Å in length, which exceeds the van der Waals length of 2.80 Å for Cu−Cu bond (SI, Figure S11, Table S5). 30,31 This suggests a metallic bond between the apex and three base atoms but nonbonding interactions between the three base atoms. The Cu 5 core unit geometry is bipyramidal, constructed by two apex coppers and three copper atoms aligned in a triangular plane that is centered between the apex coppers (SI, Figure S12).…”

Catalyzed assembly of hollow silver-sulfide cluster through self-releasable anion template

“…Combining structural analyses and kinetics investigation, we can conclude that the CO 3 2− anion acts as a self-releasable template and accelerates the formation process of 1 in a way similar to a catalyst, which is essentially different from the conventional templates that cannot be removed or can only be removed by extra post-synthesis methods [53][54][55][56] . Since the formation processes of supramolecular clusters are usually referred to molecular assembly 22,28,31 , which mainly involve reversible coordination bonding 57 , we prefer to classify the as-described process in this work as a catalyzed assembly (catassembly) process 58 .…”