Copper halide-chalcogenoether and -chalcogenone networks: Chain and cluster motifs, polymer dimensionality and photophysical properties

2,2′-Ethylenebis(1,3-dithiane) as a polydentate μ2-, μ4- and μ5-assembling ligand for the construction of sulphur-rich Cu(i), Hg(ii) and heterometallic Cu(i)/Hg(ii) coordination polymers featuring uncommon network architectures

“…In the case of the complexation with Cu(I) salts, in all cases, the formation of stable coordination polymers is observed, but a rational control of the network architecture is a difficult task. 8,70 As already noticed in previous papers and by other research groups working on Cu(I)•thioether compounds, the outcome depends on too many factors like the nature of the halide, metal-to-ligand ratio, reaction temperature, choice of the solvent, order of the addition of the reactants, etc. But this unpredictability also opens the possibility to isolate and characterize hitherto unknown network architectures, as it is the case in the present study.…”

“…Though the results of the self-assembly process are difficult to predict, Schlachter et al have recently reviewed networks built upon chalcogenoether and chalcogenone assemblies, providing some very interesting trends based on the architecture of the assembling ligands and the nature of the halide. 8 In particular, for sensing applications, the design of porous 3D CP materials plays a crucial role. One may expect that the construction of high-dimensional CPs and MOFs is favoured using tridentate or tetradentate ligands.…”

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

“…One key difference is that when globular SBUs are formed, the CPs are found to be strongly emissive ( i.e. , Φ e ≥ 10%), and when quasi-planar SBUs are generated, the isolated network is found to be weakly or not emissive . One exception was recently reported for a 3D-CP [(Cu 8 I 8 )­( L4 ) 2 ] n ( CP4 ) formed when CuI was reacted with para -MeOC 6 H 4 S­(CH 2 ) 4 SC 6 H 4 OMe ( L4 ) in which a very rare 1D-SBU (Cu 8 I 8 ) n as a poly­(truncated rhombic dodecahedron) formed .…”

“…Concurrently, chalcogenoether and chalcogenide ligands also form an important class of one-dimensional (1D)-, two-dimensional (2D)-, and three-dimensional (3D)-CPs when reacted with copper­(I) halides . Indeed, these networks also exhibit rich properties such as solid-to-solid phase transition, vapo-, solvato-, and thermochromism, photo- and electroluminescence, redox activity, (semi)­conductivity, porosity, gas adsorption, cytotoxicity, and antibacterial behaviors, leading to applications such as solar cells, light-emitting diodes, heterogeneous catalysis, photocatalysis, stimuli-responsive smart and self-healing materials, sensors, and cancer therapy .…”

Structural characterization and luminescence properties of trigonal Cu(i) iodine/bromine complexes comprising cation–π interactions

“…Copper(I) halide complexes have attracted a large amount of attention as a new class of promising emissive metal complexes due to their rich structural diversity, outstanding photophysical behavior and relatively low-cost compared to their noble metal counterparts. [1][2][3][4] In particular, high photoluminescence quantum yields (PLQYs) approaching 100% are possible for the Cu(I) complexes as no internal quenching processes of excited states via low-lying metal-centered d-d* states take place in contrast to other 3d element (Ru II , Pt II and Ir III ) compounds. [5][6][7] Previous reports have indicated that Cu(I)-based complexes with different types of coordinated ligands are able to achieve remarkable luminescence characteristics, including room temperature phosphorescence (RTP) and thermally activated delay fluorescence (TADF).…”