期刊
INORGANIC CHEMISTRY
卷 60, 期 7, 页码 5333-5342出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.1c00318
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Hybrid bismuth-containing halides are considered as alternative candidates to lead-containing perovskites for light-harvesting applications due to their similar electronic structures and outstanding charge-carrier transport properties. A family of materials has been prepared with different ligands, and the presence of copper and potassium in the reactions has influenced the crystal structures and optical properties of the resulting compounds.
Hybrid bismuth-containing halides are emerging as alternative candidates to lead-containing perovskites for light-harvesting applications, as Bi3+ is isoelectronic with Pb2+ and the presence of an active lone pair of electrons is expected to result in outstanding charge-carrier transport properties. Here, we report a family of one binary and three ternary iodobismuthates containing 1,4-diazabicyclo[2.2.2]octane (DABCO). These materials have been prepared solvothermally and their crystal structures, thermal stability, and optical properties determined. Reactions carried out in the presence of bismuth iodide and DABCO produced (C6H12N2)BiI3 (1), which consists of hybrid ribbons in which pairs of edge-sharing bismuth octahedra are linked by DABCO ligands. Short I center dot center dot center dot I contacts give rise to a three-dimensional network. Similar reactions in the presence of copper iodide produced (C8H17N2)(2)Bi2Cu2I10 (2) and [(C6H13N2)(2)BiCu2I7](C2H5OH) (3) in which either ethylated DABCO cations (EtDABCO)(+) or monoprotonated DABCO cations (DABCOH)(+) are coordinated to copper in discrete tetranuclear and trinuclear clusters, respectively. In the presence of potassium iodide, a unique three-dimensional framework, (C6H14N2)[(C6H12N2)KBiI6] (4), was formed, which contains one-dimensional hexagonal channels approximately 6 angstrom in diameter. The optical band gaps of these materials, which are semiconductors, range between 1.82 and 2.27 eV, with the lowest values found for the copper-containing discrete clusters. Preliminary results on the preparation of thin films are presented.
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