Dehnhardt Natalie, Paneth Hayden, Hecht Nikolas, Heine Johanna
Department of Chemistry and Material Sciences Center, Philipps-Universität Marburg, 35043 Marburg, Germany.
Department of Chemistry, Union College, Schenectady, New York 12308, United States.
Inorg Chem. 2020 Mar 16;59(6):3394-3405. doi: 10.1021/acs.inorgchem.9b03287. Epub 2020 Feb 20.
Both lead halide perovskites and bismuth-based double perovskites have generated intense research interest in the past few years. There is, however, a broader class of bismuthates that transcends the double perovskite motif. These multinary halogenido bismuthates remain severely underexplored and offer rich research opportunities with regard to new structure motifs and material properties. In this Forum Article, we want to provide both an overview of the work on this class of compounds that has been done in the last 2 decades and an example of how new compounds can be obtained and which challenges are associated with their synthesis. We present the synthesis and characterization of six new bismuthates, (PBz)BiBr () (PBz)(MeCN)CuBiBr (), (PBz)BiI (), (PBz)(MeCN)CuBiI (), (PBz)AgBiI (), and (PBz)BiI·CHO (), based on the tetrabenzylphosphonium cation PBz. , , and represent new multinary bismuthates, featuring both a familiar anion motif with a new element combination in and a previously unknown anionic chain in . We use this series of compounds to further elucidate the influence of the anion composition, nuclearity, and dimensionality on the compounds' onset of absorption and discover that an additional factor, the connectivity between coordination polyhedra, plays a role in copper iodido bismuthates.
在过去几年中，卤化铅钙钛矿和铋基双钙钛矿都引起了广泛的研究兴趣。然而，有一类更广泛的铋酸盐超越了双钙钛矿结构。这些多元卤化铋酸盐仍未得到充分研究，在新的结构模式和材料特性方面提供了丰富的研究机会。在这篇论坛文章中，我们既想概述过去20年中关于这类化合物的研究工作，又想举例说明如何获得新化合物以及它们的合成面临哪些挑战。我们展示了六种基于四苄基鏻阳离子PBz的新铋酸盐的合成与表征，即(PBz)BiBr ()、(PBz)(MeCN)CuBiBr ()、(PBz)BiI ()、(PBz)(MeCN)CuBiI ()、(PBz)AgBiI ()和(PBz)BiI·CHO ()。 、 和 代表新的多元铋酸盐， 在 中具有熟悉的阴离子模式和新的元素组合， 在 中具有以前未知的阴离子链。我们利用这一系列化合物进一步阐明阴离子组成、核数和维度对化合物吸收起始的影响，并发现另一个因素，即配位多面体之间的连接性，在碘化铜铋酸盐中起作用。
