A Copper-Rich Multinary Iodido Bismuthate with Cationic Ligands and Broad Red Emission

IF 7.2 2区材料科学 Q2 CHEMISTRY, PHYSICAL

Chemistry of Materials Pub Date : 2025-05-23 DOI:10.1021/acs.chemmater.5c00306

Jakob Möbs, Philip Klement, Lukas Gümbel, Paula Epure, Florian Weigend, Sangam Chatterjee, Johanna Heine

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Abstract

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)₄BiCu₄I₁₁·2MeCN (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 (H₂piz)CuI₃ and (H₂piz)Bi₂I₈ 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.

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一种含阳离子配体的富铜多元铋酸碘及其宽红光发射

卤化铅钙钛矿和相关的杂化金属卤化物具有优异的半导体性能，可在光伏、固态照明和光催化等领域实现多种应用。多卤代金属酸盐结合多种金属，为调整这些材料的光学和电子特性提供了独特的机会，以适应特定的应用。本文介绍了迄今为止报道的最富铜的分子铋酸碘（Hpiz）4BiCu4I11·2MeCN （piz =哌嗪）的合成和表征，其Cu/Bi比为4:1。它将盐铜酸盐与阳离子配体的“一体化”设计理念扩展到多体系，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，使其成为光收集和近红外发射应用的有希望的候选材料。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（H2piz）CuI3和（H2piz）Bi2I8揭示了异质金属相互作用在调制光学性质中的作用。这项研究为铜铋碘化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。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Chemistry of Materials 工程技术-材料科学：综合

CiteScore

14.10

自引率

5.80%

发文量

929

审稿时长

1.5 months

期刊介绍： The journal Chemistry of Materials focuses on publishing original research at the intersection of materials science and chemistry. The studies published in the journal involve chemistry as a prominent component and explore topics such as the design, synthesis, characterization, processing, understanding, and application of functional or potentially functional materials. The journal covers various areas of interest, including inorganic and organic solid-state chemistry, nanomaterials, biomaterials, thin films and polymers, and composite/hybrid materials. The journal particularly seeks papers that highlight the creation or development of innovative materials with novel optical, electrical, magnetic, catalytic, or mechanical properties. It is essential that manuscripts on these topics have a primary focus on the chemistry of materials and represent a significant advancement compared to prior research. Before external reviews are sought, submitted manuscripts undergo a review process by a minimum of two editors to ensure their appropriateness for the journal and the presence of sufficient evidence of a significant advance that will be of broad interest to the materials chemistry community.