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Multinary Halogenido Bismuthates beyond the Double Perovskite Motif
Natalie Dehnhardt1, Hayden Paneth2, Nikolas Hecht3
1Department of Chemistry and Material Sciences Center, Philipps-Universität Marburg, 35043 Marburg, Germany.
Inorganic Chemistry
|February 21, 2020
Summary
This study explores underexplored multinary bismuthates, synthesizing six new compounds. Researchers discovered new anionic structures and factors influencing their optical properties, expanding the field of bismuthate materials.
Area of Science:
- Materials Science
- Inorganic Chemistry
- Solid-State Chemistry
Background:
- Lead halide perovskites and bismuth-based double perovskites are well-researched.
- A broader class of multinary halogenido bismuthates remains underexplored.
- These materials offer opportunities for novel structures and properties.
Purpose of the Study:
- To provide an overview of research on multinary bismuthates over the last two decades.
- To demonstrate methods for synthesizing new bismuthate compounds.
- To investigate the challenges in bismuthate synthesis and characterization.
Main Methods:
- Synthesis and characterization of six new bismuthates using the tetrabenzylphosphonium cation (PBz4+).
- Crystallographic analysis to determine structures, including new anionic motifs.
- Optical absorption spectroscopy to study material properties.
Main Results:
- Six new bismuthates were synthesized: (PBz4)3Bi3Br12 (1), (PBz4)2(MeCN)2Cu2Bi2Br10 (2), (PBz4)Bi2I7 (3), (PBz4)2(MeCN)2Cu2Bi2I10 (4), (PBz4)2AgBi2I9 (5), and (PBz4)3Bi3I12·C4H8O (6).
- Compounds 2, 4, and 5 represent novel multinary bismuthates, with 5 featuring a previously unknown anionic chain.
- Anion composition, nuclearity, and dimensionality influence optical absorption, with coordination polyhedron connectivity also playing a role in copper iodido bismuthates.
Conclusions:
- Multinary halogenido bismuthates represent a promising area for materials discovery.
- The synthesis of new compounds expands the known structural diversity of bismuthates.
- Understanding structure-property relationships is crucial for designing new bismuthate materials with desired optical characteristics.
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