Copper(I), as a d10 metal, is a promising affordable non‐critical raw material finding great interest for the development of photoluminescent materials. Halide and thiolatebased copper(I) compounds are known for their efficient emission and good stability. In order to rationalize the effect of these two anions in the structure and photoemission of Cu(I) compounds, two new families of coordination polymers have been synthesized: the copper(I)‐thiolates: [Cu(p‐SPhX)]n (X = F, Cl, Br), and the copper halide thiolates : [Cu3Cl(p‐SPhX)2]n (X = F, Cl, Br). The two families display different structural dimensionalities: 1D [Cu(p‐SPhX)]nvs. 2D [Cu3Cl(p‐SPhX)2]n and they exhibit distinct photophysical properties: [Cu(p‐SPhX)]n show usual solid‐state red emission, while [Cu3Cl(p‐SPhX)2]n have intense solid‐state green anti‐Stokes emission, associated, for the non‐centrosymmetric compounds, X = F and Br, to non‐linear optical response (NLO), pointing out the effect of the weak halogen interactions of the thiolate ligands on the symmetry and the properties.

中文翻译：

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红色发射的 1D 铜 （I） 硫醇酸盐和绿色发射的 2D 卤化铜 （I） 硫酸盐显示二次谐波产生和双光子吸收过程


铜 （I） 作为 d10 金属，是一种很有前途且价格合理的非关键原材料，对光致发光材料的开发产生了极大的兴趣。卤化物和硫代铜 （I） 化合物以其高效的发射和良好的稳定性而闻名。为了合理化这两个阴离子对 Cu（I） 化合物结构和光发射的影响，已经合成了两个新的配位聚合物系列：铜 （I）-硫代酸酯：[Cu（p-SPhX）]n （X = F， Cl， Br），卤化铜硫醇酸盐：[Cu3Cl（p-SPhX）2]n （X = F， Cl， Br）。这两个族显示不同的结构尺寸： 1D [Cu（p‐SPhX）]nvs.2D [Cu3Cl（p‐SPhX）2]n 和它们表现出不同的光物理性质：[Cu（p‐SPhX）]n 显示通常的固态红色发射，而 [Cu3Cl（p‐SPhX）2]n 具有强烈的固态绿色反斯托克斯发射，对于非中心对称化合物 X = F 和 Br，与非线性光学响应 （NLO） 相关，指出了硫代化物配体的弱卤素相互作用对对称性和性质的影响。