Electronic structures and optical properties of (Ph4P)MX2 (M = Cu, Ag; X = Cl, Br)

Quasi-linear CuX2(X = Cl, Br) motif-built hybrid copper halides realizing encouraging nonlinear optical activities

“…It's noteworthy that most of the previously reported copper halides containing linear copper–halide units crystallized in the CS space groups, and linear anionic halide frameworks have been rarely reported until now. 32–34,41,42 The phase purities of 1 and 2 were verified by powder X-ray diffraction (XRD) analysis, which are in good agreement with the simulated ones (Fig. 1e).…”

“…[26][27][28][29][30][31] Furthermore, the exploration of NLO properties in hybrid copper halides with linear units in reported noncentrosymmetric (NCS) structures is lacking. [32][33][34] Therefore, it remains a challenge to design and synthesize Cu(I)-based hybrids with linear units [CuX 2 ] and phase-matchable NLO behaviour. In this study, by assembling an asymmetric organic molecule [(C 6 H 5 ) 3 PC 2 H 5 X] with a d 10 transition-metal cation, we obtained two polar low-toxicity copper(I) halide materials, (C 20 H 20 P)CuX 2 (X = Cl (1), Br (2)), which are composed of a quasi-linear [CuX 2 ] − unit and [C 20 H 20 P] + cations.…”

Ultrabright Light Emission Properties of All-Inorganic and Hybrid Organic–Inorganic Copper(I) Halides

“…With this question in mind, we prepared and characterized (Ph 4 P)MX 2 (Ph 4 P + = tetraphenylphosphonium; M = Cu, Ag; X = Cl, Br), which exhibit 0D crystal structures featuring isolated linear [CuX 2 ] − and dimeric [Ag 2 Cl 4 ] 2− anions made of edge-sharing approximate trigonal planar units. 63 The utilization of the bulky Ph 4 P + cations ensures the complete isolation of inorganic molecular anions with the nearest distances between the metal centers in isolated anions higher than 7.1 Å. However, despite the maximized charge localization, (Ph 4 P)MX 2 are found to be rather weak light emitters with the estimated PLQY values of ∼1%.…”

“… ,,− Since alkali copper­(I) halide structures are based on tetrahedral [CuX 4 ] building blocks, perhaps the first question is if nontetrahedral Cu­(I) halides are also luminescent. With this question in mind, we prepared and characterized (Ph 4 P)­MX 2 (Ph 4 P + = tetraphenylphosphonium; M = Cu, Ag; X = Cl, Br), which exhibit 0D crystal structures featuring isolated linear [CuX 2 ] − and dimeric [Ag 2 Cl 4 ] 2– anions made of edge-sharing approximate trigonal planar units . The utilization of the bulky Ph 4 P + cations ensures the complete isolation of inorganic molecular anions with the nearest distances between the metal centers in isolated anions higher than 7.1 Å.…”

Highly Efficient White Emission from Semiconductor Ink Based on Copper Iodide Nanoclusters

“…Low-dimensional metal halide semiconductors, particularly lead-based hybrid perovskites, have captured tremendous attention recently and rapidly advanced the light-emitting field because of their unique photophysical properties, structural variety, and solution processability. − Unfortunately, the instability of lead halide perovskites to moisture and heat, as well as the potential toxicity of lead, severely restricts their practical applications. − Meanwhile, lead-based perovskites usually require complex anion and/or ligand exchanges to achieve single-compound white light illumination . This has led to the progressive emergence of alternative lead-free hybrid materials with various optically active metal centers, including Sn­(II), Sb­(III), Bi­(III), Zn­(II), and others. − Among them, copper­(I) halide-based hybrids are recognized for their low toxicity, earth abundance, and rich structural chemistry and are considered promising candidates for future lighting technologies. − …”