Dehnhardt Natalie, Klement Philip, Chatterjee Sangam, Heine Johanna
Department of Chemistry and Material Sciences Center , Philipps-Universität Marburg , Hans-Meerwein-Straße, 35043 Marburg , Germany.
Institute of Experimental Physics I and Center for Materials Research (ZfM) , Justus Liebig University Giessen , Giessen , Germany.
Inorg Chem. 2019 Aug 19;58(16):10983-10990. doi: 10.1021/acs.inorgchem.9b01466. Epub 2019 Aug 7.
Multinary organic-inorganic metal halide materials beyond the perovskite motif can help to address both fundamental aspects such as the electronic interactions between different metalate building units and practical issues like stability and ease of preparation in this new field of research. However, such multinary compounds have remained quite rare for the halogenido pentelates, as the formation of simpler side phases can be a significant hindrance. Here, we report a family of four new multinary iodido pentelates [PPh][ECuI(nitrile)] (E = Sb, Bi; nitrile = acetonitile or propionitrile), including the first metalate with a Cu-I-Sb unit. The compounds can be obtained by facile solution or mechanochemical methods and display good stability up to 160 °C. A comparison with compounds containing binary anions [EI] reveals that, unexpectedly, the addition of the iodido cuprate unit causes a blue-shift in the absorption of the antimonates but a red-shift in the bismuthates. Photoluminescence investigations at 10 K show that the compounds display broad luminescence bands that correspond well with the trend in their onset of absorption. Overall, the work highlights that multinary, non-perovskite halogenido metalates can be a valuable expansion of the chemistry of metal halide perovskites.
超越钙钛矿结构的多元有机-无机金属卤化物材料有助于解决一些基本问题，比如不同金属酸盐结构单元之间的电子相互作用，以及在这个新研究领域中的实际问题，如稳定性和制备的简易性。然而，对于卤代五价金属酸盐来说，这种多元化合物仍然相当罕见，因为较简单的副相的形成可能是一个重大障碍。在此，我们报道了四种新型多元碘代五价金属酸盐[PPh][ECuI(腈)]（E = Sb、Bi；腈 = 乙腈或丙腈）的系列，其中包括首个含有Cu-I-Sb单元的金属酸盐。这些化合物可以通过简便的溶液法或机械化学方法获得，并且在高达160°C的温度下表现出良好的稳定性。与含有二元阴离子[EI]的化合物的比较表明，出乎意料的是，碘代铜酸盐单元的加入导致锑酸盐的吸收发生蓝移，而铋酸盐的吸收发生红移。在10K下的光致发光研究表明，这些化合物显示出宽的发光带，与它们吸收起始的趋势很好地对应。总体而言，这项工作突出表明，多元、非钙钛矿卤代金属酸盐可以是金属卤化物钙钛矿化学的一个有价值的扩展。
