Assembly of Cu(I) Alkynyl Complexes: From Cluster to Infinite Cluster-Based Framework

Abstract

Variation of the reaction conditions with Cu powder, Cu(NO 3 ) 2 , and t BuCCH as starting materials afforded three new Cu(I) alkynyl complexes, namely, [Cu 14 ( t BuCC) 10 (NO 3 ) 4 (MeOH) 2 ]•H 2 O (1), Cu 15 ( t BuC C) 14 (NO 3 ) (2), and [Cu 14 ( t BuCC) 8 (NO 3 ) 2 (CN) 4 ] n (3). Single-crystal X-ray analysis revealed that clusters 1 and 2 consist of Cu 14 and Cu 15 cores costabilized by strong by σand π-bonded tert-butylethynides and nitrates. Complex 3 displays an intriguing three-dimensional cyano-bridged Cu(I) alkynyl cluster-based framework, in which the existence of CN − is assumed to have originated from the Cu(I)-mediated C−C cleavage reaction of acetonitrile under mild solvothermal conditions.

Copper(I) Alkynyl Clusters with Crystallization-Induced Emission Enhancement

“…Metal clusters have attracted much interest in view of their structural diversity and potential use for applications. − Among them, Au and Ag clusters have been long studied because of their higher stability and biocompatibility. − However, in contrast to significant research progress in Au and Ag clusters, Cu­(I) is more sensitive and easier to oxidize, which makes it more challenging to prepare Cu­(I) clusters and investigate their properties. − Recently, the synthesis of stable Cu clusters with well-defined structure and luminescence has drawn intense attention of researchers. − …”

Carboxylate Ligand‐supported Agn (n=21 and 24) Alkynyl Clusters Induced by Single/Double Carbonate Ions

“…As shown in Figure 6, compounds 1 and 2 have absorption in the range of 200–500 nm, with the maximum absorption peak located at 290 nm and 275 nm, respectively [75] . The absorption of compounds 1 and 2 can be assigned to π→π* and ligand‐to‐metal charge transfer within the tert ‐butylacetylene ligand [76–78] . According to the Kubelka–Munk methods, the bandgaps of 1 and 2 were estimated as 2.86 and 3.51 eV, respectively.…”

“…[75] The absorption of compounds 1 and 2 can be assigned to π!π* and ligand-to-metal charge transfer within the tert-butylacetylene ligand. [76][77][78] According to the Kubelka-Munk methods, the bandgaps of 1 and 2 were estimated as 2.86 and 3.51 eV, respectively.…”

Unsymmetrical Naphthyridine-Based Dicopper(I) Complexes: Synthesis, Stability, and Carbon–Hydrogen Bond Activations

“…54 This complex is stable under wet conditions but highly explosive if dry. In the absence of any additional ligand, the copper alkynyl adopts a polymeric form, 55,56 which confers it a thermal and shock stability, contrary to the earlier complexes. In presence of a Lewis base (phosphine, carbine, amine, etc.…”