Properties and applications of copper halide-chalcogenoether and -chalcogenone networks and functional materials

Abstract

Copper(i) halides form, with chalcogenoethers and chalcogenones, 0–3D coordination materials containing CuxXxEy clusters (E = S, Se, Te; X = Cl, Br, I; x = 2–8), and exhibit rich properties and applications.

A Fused Poly(truncated rhombic dodecahedron)-Containing 3D Coordination Polymer: A Multifunctional Material with Exceptional Properties

“…These SBUs are then fused together to form parallel columnar-[CuI] n globular chains. It is also worth noting that the formation of 3D networks of Cu x X x L y materials (X = Cl, Br, I; x = 2–8; 4 < y < 8) is rare. − The 4-methoxythiophenyl groups (not shown in Figure ) are filling the cavities inside the macrocycles, which adapt by changing their quasi-planar geometry for a twisted one where both C–S–C bonds have rotated. The dimensions of these cavities are defined by the SBU center-to-SBU center within the diamond, which are 12.509, 13.073, and 15.565 Å, Figure S5) making this polymer nonporous (analyses, i.e., vdW surface, void space %, and void space, using CrystalMaker, are provided in Figure S6).…”

“…In Figure , a schematic representation illustrating the origin of the separated Cu 4 I 4 cubanes in CP1 is provided in different colors. In the category of [Cu x X x L y ] compounds (X = Cl, Br, I; x = 2–8; 4 < y < 8; L = thioether), this template effect is unprecedented. − Moreover, CP2 exhibits no evidence for aging even after several months.…”

“…Nowadays, the design of new materials focuses on introducing this motif or higher-nuclear derivatives (i.e., Cu x X x L y ; X = Cl, Br, I; x = 2–8; 4 < y < 8) inside 1D, 2D, and 3D coordination polymers through the use of bi- and polydentate ligands. In parallel, the replacement of the N - and P -donor homo-ligands by chalcogenoethers (literature reveals that the S -donor ligands are the most reported) also leads to 1D, 2D, and 3D coordination polymers. − From these networks, a large range of applications have emanated including luminescent sensors; − light emitting diodes; dye sensitized solar cells; , homo- − and heterogeneous , thermo-, electro-, and photocatalysts; and self-healing materials. , Many of these properties stem from the redox-active couple (Cu­(I) → Cu­(II) + 1e – ) and luminescent clusters often designated as secondary building units (SBUs), and a few structure-property relationships have been shown. For instance, the two most encountered SBU motifs are the Cu 4 I 4 L 4 cubane and Cu 2 I 2 L 4 rhomboid (>80% of occurrence), − respectively, belonging to globular and quasi-planar motifs.…”

“…In parallel, the replacement of the N - and P -donor homo-ligands by chalcogenoethers (literature reveals that the S -donor ligands are the most reported) also leads to 1D, 2D, and 3D coordination polymers. − From these networks, a large range of applications have emanated including luminescent sensors; − light emitting diodes; dye sensitized solar cells; , homo- − and heterogeneous , thermo-, electro-, and photocatalysts; and self-healing materials. , Many of these properties stem from the redox-active couple (Cu­(I) → Cu­(II) + 1e – ) and luminescent clusters often designated as secondary building units (SBUs), and a few structure-property relationships have been shown. For instance, the two most encountered SBU motifs are the Cu 4 I 4 L 4 cubane and Cu 2 I 2 L 4 rhomboid (>80% of occurrence), − respectively, belonging to globular and quasi-planar motifs. The former category, which includes hexagonal prism − and fused dicubane, − is systematically strongly luminescent, whereas the rhomboid motif is mostly either weakly emissive or non-emissive (but not exclusively as rare examples exist) .…”

“…In the quest of designing new copper halide/thioether coordination polymers with interesting properties and potential applications and in link with our previous study on PhS­(CH 2 ) 4 SPh, this work reports two coordination polymers, 1D-[Cu 4 I 4 ( L1 )­(MeCN) 2 ] n , CP1 , and 3D-[Cu 8 I 8 ( L1 ) 2 ] n , CP2 ( L1 = ArS­(CH 2 ) 4 SAr; Ar = 4-C 6 H 4 OMe). CP2 is quite unusual for multiple reasons.…”