Möbs Jakob, Klement Philip, Gümbel Lukas, Epure Paula, Weigend Florian, Chatterjee Sangam, Heine Johanna
Department of Chemistry and mar.quest|Marburg Center for Quantum Materials and Sustainable Technologies, Philipps-Universität Marburg, Hans-Meerwein-Straße, Marburg D-35043, Germany.
Department of Physics, University of Oxford, Parks Road, OX1 3PU Oxford, U.K.
Chem Mater. 2025 May 23;37(11):4038-4046. doi: 10.1021/acs.chemmater.5c00306. eCollection 2025 Jun 10.
Lead halide perovskites and related hybrid metal halides exhibit exceptional semiconductor properties, enabling diverse applications in photovoltaics, solid-state lighting, and photocatalysis. Multinary halido metalates, combining multiple metals, offer unique opportunities to tune the optical and electronic properties of these materials for specific applications. Here, we present the synthesis and characterization of (Hpiz)BiCuI·2MeCN (piz = piperazine), the most copper-rich molecular iodido bismuthate reported to date, featuring a Cu/Bi ratio of 4:1. It extends the "all-in-one" design concept of halido cuprates with cationic ligands to multinary systems and exhibits a low optical band gap of 1.82 eV (681 nm) and broad red photoluminescence centered at 1.69 eV (735 nm), making it a promising candidate for light-harvesting and near-infrared emission applications. Quantum chemical analyses attribute the reduced band gap to strong electronic interactions between Cu-(I) and Bi-(III). Additionally, the monometallic analogs (Hpiz)-CuI and (Hpiz)-BiI reveal the role of heterometallic interactions in modulating the optical properties. This study provides valuable insights into the design of copper-bismuth iodide systems, enriching the library of hybrid materials with customized semiconductor characteristics.
卤化铅钙钛矿及相关混合金属卤化物表现出优异的半导体性能，使其在光伏、固态照明和光催化等领域有多种应用。包含多种金属的多元卤基金属酸盐为针对特定应用调整这些材料的光学和电子性质提供了独特机会。在此，我们展示了(Hpiz)BiCuI·2MeCN（piz = 哌嗪）的合成与表征，它是迄今为止报道的铜含量最高的分子碘化铋酸盐，铜铋比为4:1。它将具有阳离子配体的卤化铜酸盐的“一体化”设计概念扩展到多元体系，并且具有1.82 eV（681 nm）的低光学带隙和以1.69 eV（735 nm）为中心的宽红色光致发光，使其成为光捕获和近红外发射应用的有前途的候选材料。量子化学分析将带隙减小归因于Cu-(I)和Bi-(III)之间的强电子相互作用。此外，单金属类似物(Hpiz)-CuI和(Hpiz)-BiI揭示了异金属相互作用在调节光学性质中的作用。这项研究为碘化铜铋体系的设计提供了有价值的见解，丰富了具有定制半导体特性的混合材料库。
