Luminescence in Functionalized Copper Thiolate Clusters – Synthesis and Structural Effects

Abstract

Keywords: Cluster compounds / Copper / S ligands / LuminescenceA series of luminescent polynuclear copper(I) phenyl thiolate clusters with functional groups in the organic ligand shell has been synthesized and characterized by single-crystal X-ray diffraction. Cluster compounds 1-5 with Me 2 N groups bound to the phenyl thiolate are described and feature different nuclearities and core geometries. The heptanuclear compound 6, which contains both phenyl thiolate and Me 3 SiO functionalized phenyl thiolate ligands, is an unusual example of a mixed thiolate cluster and exhibits a core almost identical to that of 5. The optical properties of these compounds, which range from binuclear complexes with large Cu···Cu distances to cluster molecules with seven copper atoms and relatively [a] www.eurjic.org FULL PAPER stances exhibit luminescence upon irradiation with UV light, their optical properties were investigated in detail and the influence of size, structure and the functional group in the para position on these properties are discussed.

Copper(I) Thiolate Heteroadamantane Cage Structures with Relevance to Metalloproteins

“…[7,11,12] Although the structure of Cu A and its biological functions are well-known, the incorporation of copper in the proteins and, in particular, the formation of the mixed-valent dinuclear centre is one of the remaining challenges in understanding Cu A . This assembly proceeds through several different types of mononuclear copper centres, and a new intermediate Cu(Cys) 2 His complex has been identified recently. [13] Many attempts have been performed to model biomimetically this dinuclear fully delocalised class III system Cu A .…”

“…Copper complexes with sulfur ligands and additional N‐donor functions are of large interest owing to their abundance in biological systems . They have received much attention for their photochemical properties, synthetic usage and applications in materials science . This is founded on the ability to stabilise a variety of structural motifs, in metal sulfur compounds and on their electrochemical potentials within the biological range .…”

Synthesis and Characterization of “Atlas-Sphere” Copper Nanoclusters: New Insights into the Reaction of Cu2+ with Thiols

“…For example, the "Atlas-sphere" clusters, [Cu12E6L8] (E = S, Se; L = phosphine), are strongly luminescent, with measured PL quantum yields of up to 90%. [52][53][54] In fact, many Cu(I)-containing clusters are known to be photoluminescent, 13,[82][83][84][85][86][87][88][89] including many Cu(I)-thiolate and Cu(I)thiolate/halide clusters. 13,83,[87][88][89] For example, [Cu(SR)]n (n = 2, 4, 7; R = p-S-C6H4-NMe2) 13 features an emission peak between 480 and 560 nm, depending on its nuclearity, while [(Cu(S t Bu))4(dppe)]n (dppe = bis(diphenylphosphino)ethane) and [(CuS t Bu)6(bix)]n (bix = 1,4-bis(imidazole-1-ylmethyl)benzene) emit at 603 and 629 nm, respectively.…”

Binuclear Copper(I) Compounds with N‐Heterocyclic Thiolate and Diphosphane Ligands: Effects of Thiolate Ligands on Solid‐State Molecular Structures and Luminescence Properties

“…Experimental and theoretical data reveal the existence of a strong relationship between the emission properties and core structures as well as geometrical characteristics of Cu I complexes . Thiol or thiolate ligands, owing to their ability of the S‐donor atom to bridge different metal centers and to yield complexes with variable nuclearity and structural complexity, appear to be a very interesting class of ligands for the synthesis of photoluminescent Cu I complexes with diverse multinuclear molecular architectures.…”