journal article·2023-11-14

Self-Assemblies of Isomeric Copper Iodide Trimers with Geometry-Dependent Photophysical Properties

Linyuan Lian, Peng Zhang, Jianbo Gao, Daoli Zhang, Jianbing Zhang

Chemistry of Materials· Volume 35· Issue 21
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Abstract

Zero-dimensional (0D) metal halides have attracted great research interest for the past few years due to their fascinating photophysical properties and extraordinary structural diversity. However, controlled synthesis of these metal halides in a rational way remains a big challenge, and the basic relationship between their crystal structures and photophysical properties is still not well understood. In this work, two new 0D self-assemblies of isomeric copper iodide trimers with the same formula of (BTMA) 3 Cu 3 I 6 (BTMA = benzyltrimethylammonium) but different crystal structures were synthesized. Interestingly, we found that the photophysical properties of these copper iodide isomers depend strongly on the geometries of their copper iodide trimers, i.e., one isomer with boat-shaped [Cu 3 I 6 ] 3– trimers ( T1 ) exhibits yellow emission centered at 606 nm at room temperature, while the other isomer with crown-shaped [Cu 3 I 6 ] 3– trimers ( T2 ) shows orange emission centered at 639 nm. Density functional theory (DFT) calculations revealed that both the organic cations and inorganic copper iodide trimers participate in the luminescence process of these copper iodide isomers, and a through-space charge transfer (TSCT) between the spatially separated organic ligands and inorganic [Cu 3 I 6 ] 3– trimers would occur during the optical emission/absorption, which is quite different from the luminescence mechanism proposed for the previously reported 0D ionic copper halides.
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Research context

OpenAlex topics: Perovskite Materials and Applications · Advanced Photocatalysis Techniques · Metal-Organic Frameworks: Synthesis and Applications

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

Affiliations

Key Laboratory of Materials Physics of Ministry of Education, School of Physics and Microelectronics, Zhengzhou University, Zhengzhou 450052, China

School of Integrated Circuits, Wuhan National Laboratory for Optoelectronics, Huazhong University of Science and Technology, Wuhan, Hubei 430074, China

Key Laboratory of Optoelectronic Devices and Systems of Ministry of Education and Guangdong Province, College of Physics and Optoelectronic Engineering, Shenzhen University, Shenzhen 518060, China

Department of Chemistry, Brock University, St. Catharines, ON L2S 3A1, Canada

Shenzhen Huazhong University of Science and Technology Research Institute, Shenzhen, Guangdong 518057, China

Wenzhou Advanced Manufacturing Technology Research Institute, Huazhong University of Science and Technology (HUST), Wenzhou, Zhejiang 325035, China

Funding

National Key Research and Development Program of China · Science, Technology and Innovation Commission of Shenzhen Municipality · National Natural Science Foundation of China · Guangdong Basic and Applied Basic Research Foundation · Shenzhen Science and Technology Program · Shenzhen High-Talent Research Foundation · Key Research and Development Program of Hubei Province

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