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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
Coordination networks from a bifunctional molecule containing carboxyl and thioether groups
Xiao-Ping Zhou1, Zhengtao Xu, Matthias Zeller
1Department of Biology and Chemistry, City University of Hong Kong, 83 Tat Chee Avenue, Kowloon, Hong Kong, China.
Inorganic Chemistry
|August 8, 2008
Summary
Tetrakis(methylthio)-1,4-benzenedicarboxylic acid (TMBD) forms coordination networks with copper, cadmium, and zinc ions. The methylthio groups preferentially bind softer metal ions, influencing the electronic band gaps of the resulting networks.
Area of Science:
- Materials Science
- Coordination Chemistry
- Solid-State Chemistry
Background:
- Metal-organic frameworks (MOFs) and coordination polymers are versatile materials with tunable properties.
- The design of functional coordination networks requires understanding metal-ligand interactions.
- Bifunctional organic linkers offer unique possibilities for constructing complex structures.
Purpose of the Study:
- To investigate the coordination behavior of tetrakis(methylthio)-1,4-benzenedicarboxylic acid (TMBD) with different metal ions.
- To synthesize and characterize novel coordination networks formed by TMBD and Cu(I), Cd(II), and Zn(II).
- To explore the relationship between metal-thioether interactions and the electronic properties of the resulting solid-state networks.
Main Methods:
- Synthesis of coordination networks using TMBD and metal salts (Cu, Cd, Zn).
- Single-crystal X-ray diffraction for structural determination of the coordination networks.
- Diffuse-reflectance spectroscopy to analyze the electronic band gaps.
Main Results:
- Formation of three distinct coordination networks: Cu2TMBD, CdTMBD, and Zn4O(H2O)3(TMBD)3.
- Carboxyl groups consistently coordinate to metal ions.
- Methylthio groups exhibit selective binding: chelation to Cu(I), single-fold coordination to Cd(II), and nonbonding to Zn(II).
- Metal-thioether interactions correlate with reduced electronic band gaps in the solid-state networks.
Conclusions:
- TMBD acts as a versatile linker, forming diverse coordination networks with varying metal ions.
- The preferential binding of methylthio groups to softer metal ions is a key factor in dictating network structure.
- The observed metal-thioether interactions significantly impact the electronic properties, leading to smaller band gaps.
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