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

Abstract

A series of four photoluminescent binuclear copper(I) compounds bearing phosphorus and sulfur donor atom ligands have been synthesized from reactions of copper(I) halides with the diphosphane dppe [1,2-bis(diphenylphoshino)ethane] and the anions of three different N-heterocyclic thiols, namely 5-methyl-1,3,4-thiadiazole-2-thiol, 1-phenyl-1H-tetrazole-5-thiol and ethyl 2-thiouracil-5-carboxylate. Depending on the nature of the N-heterocyclic thiol, the resulting compounds adopt two different structural motifs, having either a dppebridged core, that is, [Cu 2 (κ-S-thiolate) 2 (dppe) 2 (μ-dppe)], or a bis(thiolate)-bridged core, that is, [Cu 2 (μ-S-thiolate) 2 (dppe) 2 ], with a Cu 2 (μ-S) 2 cluster-type core. The stabilization of the latter type of structure is rationalized by the presence of intramolecular hydrogen-bonding interactions developed between two bridging N-heterocyclic thiolate ligands positioned at the same side of the Cu 2 (μ-S) 2 core, which lead to short Cu···Cu interactions (ca. 2.6 Å), as it is evidenced by X-ray crystallography stud- [a]

Investigation of the role of hydrogen bonding in ionic liquid-like salts with both N- and S-soft donors

“…These values are similar to the free 5-methyl-1,3,4-dithiazole-2-thiol (90.0°), 48 or for example, in a mixed phenyl phosphate complex of Cu I (90.2°). 49 Table 1 Melting points and decomposition temperatures for 1-6…”

Synthesis and Characterization of Luminescent Binuclear μ‐HS Cu(I) Complexes

“…Owing to the abundant coordination modes of the S-donor ligands, some multinuclear Cu(I) molecular architectures have been constructed with interesting photoluminescence. [32][33][34][35][36][37] Herein, we reported the synthesis, characterization and physical properties of (POP) 2 Cu 2 (μ-HS/ Cl) 2 • 0.92MeOH (1) and (POP) 2 Cu 2 (μ-HS) 2 (2).…”