Structure Determination of Homoleptic Au^I, Ag^I, and Cu^I Aryl/Alkylethynyl Coordination Polymers by X‐ray Powder Diffraction

Abstract

This article describes the structure determination of five homoleptic d(10) metal-aryl/alkylacetylides [RC triple bond CM] (M=Cu, R=tBu 1, nPr 2, Ph 3; R=Ph, M=Ag 4; Au 5) by using X-ray single-crystal and powder diffraction. Complex 1.C6H6 reveals an unusual Cu20 catenane cluster structure that has various types of tBuC triple bond C-->Cu coordination modes. By using this single-crystal structure as a starting model for subsequent Rietveld refinement of X-ray powder diffraction data, the structure of the powder synthesized from CuI and tBuC triple bond CH was found to have the same structure as 1. Complex 2 has an extended sheet structure consisting of discrete zig-zag Cu4 subunits connected through bridging nPrC triple bond C groups. Complex 3 forms an infinite chain structure with extended Cu-Cu ladders (Cu-Cu=2.49(4)-2.83(2) A). The silver(I) congener 4 is iso-structural to 3 (average Ag-Ag distance 3.11 A), whereas the gold(I) analogue 5 forms a Au...Au honeycomb network with PhC triple bond C pillars (Au-Au=2.98(1)-3.26(1) A). Solid-state properties including photoluminescence, nu(C triple bond C) stretching frequencies and thermal stability of these polymeric systems are discussed in the context of the determined structures.

Advancements in the mechanistic understanding of the copper-catalyzed azide–alkyne cycloaddition

“…(Arylethynyl)- and (alkylethynyl)copper(I) compounds usually form polymeric aggregates [(RC≡CCu) n ] of low solubility [200–201]. For example, X-ray powder diffraction studies have shown the insoluble yellow (phenylethynyl)copper(I) [(PhC≡CCu) n ] to consist of an infinite Cu–Cu ladder structure ( n = ∞) [184]. Both copper ions in this ladder polymer [(PhC≡CCu) 2 ] n adopt the same μ-η 1 ,η 2 -C≡C bridging mode (Fig.…”

“…ORTEP plot [202–203] of the X-ray powder diffraction crystal structure of (phenylethynyl)copper(I) [(PhC≡CCu) 2 ] n by Che et al [184,204]. …”

Development of nanoparticle probes for multiplex SERS imaging of cell surface proteins

“…17 In order to prove this, we synthesized NPs, lacking the thiol, using phenylacetylene (see ESI †). The spectrum of these NPs was consistent with those observed for MMByne, indicating that the alkyne was binding.…”

Gold catenanes

“…It also undergoes partial dissociation to give what may be the tetramer [(AuCCR) 4 ] [30]. Complexes [(AuCCR) n ], with smaller R groups, are thought to be polymeric, and this is proved to be the case in [(AuCCPh) n ], in which honeycomb sheets of gold(I) centers are present, bridged by phenylacetylide groups [31].…”