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Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework
Published on: April 9, 2018
Multiple bismuth(III)-thioether secondary interactions integrate metalloporphyrin ligands into functional networks
Kunhao Li1, Guo Huang, Zhengtao Xu
1Department of Chemistry, The George Washington University, 725 21st Street NW, Washington, DC 20052, USA.
Inorganic Chemistry
|May 10, 2007
Summary
Researchers developed a new multidentate chelation linker using a tris(organylthiophenyl) group to build coordination networks. This linker facilitated the creation of a 2D network with zinc porphyrin and bismuth bromide, showing complex bonding and electronic interactions.
Area of Science:
- Coordination Chemistry
- Materials Science
- Supramolecular Chemistry
Background:
- Development of novel ligands is crucial for constructing advanced coordination networks.
- Multidentate ligands offer versatile coordination modes for complex architectures.
- Metalloporphyrins are key components in various functional materials.
Purpose of the Study:
- To introduce and characterize the 1,2,3-tris(organylthiophenyl) group as a novel chelation linker.
- To synthesize and investigate a two-dimensional coordination network incorporating zinc porphyrin and bismuth bromide.
- To explore the bonding patterns and electronic interactions within the novel network structure.
Main Methods:
- Synthesis of zinc(II) 5,10,15,20-tetrakis[3',4',5'-tris(methylthio)phenyl]porphyrin.
- Formation of a two-dimensional network via coordination with BiBr3.
- Characterization using diffuse-reflectance spectroscopy and analysis of Bi-S interactions.
Main Results:
- Successful synthesis of the zinc porphyrin derivative and its integration into a 2D network.
- Observation of a complex bonding pattern with six sulfur atoms forming multiple Bi-S interactions with Bi2Br6 units.
- Diffuse-reflectance spectroscopy revealed electronic interactions, indicated by a modest red-shifted feature at 1.8 eV.
Conclusions:
- The 1,2,3-tris(organylthiophenyl) group serves as an effective symmetrical, multidentate linker for coordination networks.
- The novel network exhibits unique structural features and electronic communication between the porphyrin and bismuth bromide components.
- This work expands the toolkit for designing sophisticated coordination materials with tailored properties.
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