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

[Display omitted] •Chalcogenoethers and chalcogenones build 0-3D materials with CuX salts (X = Cl, Br, I).•The secondary building units, SBUs, are either of globular or quasi-planar shapes.•These SBUs consist of Cu4I4E4 cubanes and Cu2X2E4 rhomboids, respectively.•These SBUs are respectively luminescent and weakly or non-emissive.•The average Cu···Cu distances vary Cu4I4E4 < Cu2X2E4 (X = I < X = Br < X = Cl). Copper(I) halides react with mono- and polychalcogenoethers and -chalcogenones to form 0-3D coordination materials containing neutral polynuclear CuxXxEy species (E = S, Se, Te; X = Cl, Br, I; x = 2–8) called secondary building units (SBU). These species exhibit two general types of motifs namely globular and quasi-planar. Depending on the shape of these polynuclear species and the dimensionality of the network, their properties and applications are profoundly different. In a structural point of view for instance, when X = I, and E = S, the globular family includes cubane, open cubane, fused dicubane, fused open dicubane, hexagonal prism, and 1D-polycubane. Concurrently, the quasi-planar family includes rhomboid, trinuclear cluster, step staircase, 1D-zig zag ribbon, 1D-acordeon ribbon and 1D-staircase ribbon. Both the cubane and rhomboid motifs are overwhelmingly represented (>80%). Generally, the globular species are generally strongly luminescent. In contrast, the quasi-planar family exhibits only modest intensity luminescence or no emission at all. This review provides a thorough statistical analysis of these SBUs, in a structural point of view, along with their photophysical properties.