Cubane Dimerization: Cu₄ vs Cu₈ Copper Iodide Clusters

Abstract

Copper(I) halides are well-known for their structural diversity and rich photoluminescence properties, showing great potential for the development of solidstate lighting technology. A series of four molecular copper iodide clusters based on the [Cu 4 I 4 ] cubane geometry is reported. Among them, [Cu 8 I 8 ] octanuclear clusters of rare geometry resulting from dimerization of the tetranuclear counterparts were also synthesized. Two different phosphine ligands were studied, bearing either a styrene or an ethyl group. Therefore, the effect of the dimerization and of the ligand nature on the photophysical properties of the resulting clusters is investigated. The structural differences were analyzed by single-crystal X-ray diffraction (SCXRD), solid-state nuclear magnetic resonance (NMR), infrared, and Raman analyses. Compared to the ethyl group, the styrene function appears to greatly impact the photophysical properties of the clusters. The luminescence thermochromic properties of the ethyl derivatives and the intriguing photophysical properties of the clusters with styrene function were rationalized by density functional theory (DFT) calculations. Thus, the styrene group significantly lowers in energy the vacant orbitals and consequently affects the global energetic layout of the clusters. From this study, it was found that the nuclearity of copper iodide clusters eventually has less influence on the photophysical properties than the nature of the ligand. The design of proper ligands should therefore be considered when developing materials for specific lighting applications.

Polymeric CuX coordination compounds assembled from acetylenic thioether ligands RSCH2CCCH2R (R = C6H11, t-Bu): effect of the RS-group, halide and stoichiometry on the network architecture and the luminescence properties

“…15 compares the solid-state emission and excitation spectra of CP1 and CP5 recorded at 298 and 77 K. In both cases, only a low-energy emission is observed upon excitation at about 310 nm that has been attributed to a cluster-centred excited state ( 3 CC) corresponding to transitions of mixed XMCT and MM character. 13,34,36,65–67 Note that upon decreasing the temperature, no emergence of a HE emission band corresponding to a 3 (X/M)LCT charge transfer was observed, as noticed for related S -aryl-containing cubanes. 13 Table 4 summarizes the results obtained for CP1 and CP5 and compares their photoluminescence data and mean Cu–Cu distances with those reported for others CPs containing Cu 4 I 4 SBUs namely [Cu 4 I 4 ( p -Tol)SCH 2 CCCH 2 S( p -Tol) 2 ] n and [Cu 4 I 4 ( n -Bu)S(CH 2 ) 4 S( n -Bu) 2 ] n .…”