Family of Highly Luminescent Pure Ionic Copper(I) Bromide Based Hybrid Materials

While a number of highly luminescent copper­(I) halide based hybrid materials built on coordinate bonds (Cu–L; L = N, P, S-based ligands) have been obtained, the poor structural stability largely limited their commercialization. In contrast, according to the previous studies, the ionic structures (L-free) are more stable than those built on Cu–L coordinate bonds. However, the extremely weak emission hinders their optical applications. Herein, we report a tetra-alkylammonium-cation-induced strategy for the synthesis of stable and highly luminescent ionic CuBr-based hybrid materials. It is interesting to find that the tetra-alkylammonium cations with different chains could induce diverse CuBr-based anions. Moreover, most of these CuBr-based hybrids are highly luminescent, which makes them promising candidates as an alternative to phosphors and with potential applications in sensing.

尽管目前已成功制备诸多基于配位键（coordinate bond）构建的高发光卤化亚铜(I)（copper(I) halide）杂化材料（hybrid materials），其结构单元为Cu–L，其中L为氮、磷、硫基配体（ligand），但这类材料的结构稳定性欠佳，极大限制了其商业化应用。与之相对，既往研究显示，无配体（L-free）的离子型结构比基于Cu–L配位键构建的结构具有更优的稳定性。然而，此类离子型结构的发光强度极弱，严重阻碍了其在光学领域的应用拓展。本文报道了一种四烷基铵阳离子诱导的合成策略，用于制备稳定且高发光的溴化亚铜（CuBr）离子型杂化材料。值得注意的是，不同碳链长度的四烷基铵阳离子可诱导形成多种CuBr基阴离子结构。此外，此类基于CuBr的杂化材料大多展现出优异的发光性能，有望作为荧光粉（phosphors）的替代材料，并在传感领域具备潜在应用价值。