Chain Length Effect on the Structural and Emission Properties of the CuI/Bis((4-methoxyphenyl)thio)alkane Coordination Polymers

Abstract

A systematic chain length variation of the ligand para-MeOC 6 H 4 S-(CH 2 ) m SC 6 H 4 OMe (1 ≤ m ≤ 8) was performed to study its effect on the structures and photophysical properties of the coordination polymers (CP) when reacted with CuI. Indeed, direct correlations are noted between these features and m. When m is an odd number, the secondary building unit is systematically the common closed-cubane Cu 4 I 4 cluster, rendering the material strongly luminescent (i.e., emission quantum yield, Φ e > 20%), and the CP is one-dimensional (1D). However, when m is 2, 4, and 6, the SBUs exhibit rare polymeric motifs of (Cu 2 I 2 ) n : staircase ribbon, fused poly(rhombic pseudo-dodecahedron), and accordion ribbon, respectively, and the emission intensities are either very weak (Φ e < 0.001%) or of medium intensity (Φ e ∼ 10% when m = 6). When m = 8 (i.e. the most flexible chain), the SBU is a closedcubane Cu 4 I 4 and the emission intensity is medium (Φ e ∼ 10%). A special case was observed for m = 3, where a co-crystallization of the molecular cluster Cu 4 I 4 (NCCH 3 ) 4 is observed in the lattice, which turns out to be quite important for the stability of the network.

Pseudohalide Ions as Ligands to Tune Architecture and Luminescence of Polymetallic CU(I) Assemblies

“…Indeed, in the case of derivatives C–I , very efficient nonradiative relaxation pathways due to the vibrations lying on the connecting ligands are likely taking place, which results in a weakening of the emission efficiencies of these compounds (in addition, cuprophilic are also much more intense in derivative B than in any compound of the series C – I, which also very likely is another parameter that promotes more efficient radiative relaxation processes in derivative B ). However, all in all, the photophysical properties exhibited by the series of compounds C – I are coherent regarding those recently reported in the case of RT moderately luminescent Cu­(I) assemblies ranging from TADF in the case of the derivative D to phosphorescence in the case of the other compounds C and E – I . − ,− ,,,− …”

Crystal structure of trimethyl({tris[(phenylsulfanyl)methyl]silyl}methoxy)silane and Hirshfeld surface analysis of 3-bromo-2,2-bis(bromomethyl)propan-1-ol

“…Another related structure motif could be found where the thioether groups act as bridging ligands between Cu 2 I 2 rhomboids (Schlachter et al, 2022). Wappelhorst et al 4C 5 H 9 Br 3 O and C 26 H 32 OS…”

“…Thioether ligands offer an attractive alternative to known phosphine or amine ligands. As a result of the soft property of thioethers, they coordinate to transition metals (Awaleh et al, 2008;Knaust & Keller, 2003;Knorr et al, 2012Knorr et al, , 2014Schlachter et al, 2022). Furthermore, because of its two lone pairs, sulfur can act as a bridging ligand between two metal centres and thus favour coordination polymers (Awaleh et al, 2010;Peindy et al, 2009;Schlachter et al, 2018Schlachter et al, , 2020Schlachter et al, , 2021Viau et al, 2022).…”

Synthesis of Organosilicon‐Based Thioether Ligand Class Showing Defined S‐Stereogenic Coordination in Crystalline Palladium(II) Complexes

“…Other studies on similar topics are known as well [14,27,28] . Additionally, thioethers are often used as ligands in copper(I) halide complexations as metal‐enriched coordination polymers of these compounds often exhibit luminescent properties [29–40] …”

“…[14,27,28] Additionally, thioethers are often used as ligands in copper(I) halide complexations as metal-enriched coordination polymers of these compounds often exhibit luminescent properties. [29][30][31][32][33][34][35][36][37][38][39][40] In this work, we wanted to investigate the influence of the substituent on the configurational stability of the sulphur atom by modifying the aromatic system and investigating the corresponding Pd(II) complexes by SCXRD and NMR experiments at varying temperatures.…”