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Isomeric zinc(II) triazolate frameworks with 3-connected networks: syntheses, structures, and sorption properties
Ai-Xin Zhu1, Jian-Bin Lin, Jie-Peng Zhang
1MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry & Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275, China.
Inorganic Chemistry
|March 31, 2009
Summary
Two new zinc(II) metal-azolate frameworks were synthesized, exhibiting unique network topologies and selective sorption properties. These supramolecular isomers offer insights into framework stability and pore characteristics.
Area of Science:
- Materials Chemistry
- Supramolecular Chemistry
- Coordination Chemistry
Background:
- Metal-azolate frameworks are versatile materials with tunable properties.
- Understanding structure-property relationships is crucial for designing functional materials.
- Supramolecular isomerism offers a pathway to fine-tune framework characteristics.
Purpose of the Study:
- To synthesize and characterize novel ternary zinc(II)/triazolate/X metal-azolate frameworks.
- To investigate the impact of reaction conditions on framework topology and properties.
- To explore the sorption behavior and stability of the synthesized materials.
Main Methods:
- Solvothermal synthesis of zinc(II) complexes with 3,5-dimethyl-1,2,4-triazolate (Hdmtz) and either formate (HCOO-) or fluoride (F-).
- Single-crystal X-ray diffraction for structural determination of four supramolecular isomers.
- Thermogravimetric analysis (TGA) to assess thermal stability.
- Gas sorption analysis to evaluate pore properties and selective sorption.
Main Results:
- Synthesis of two pairs of supramolecular isomers: [Zn(dmtz)(HCOO)]·xH2O (1a, 1b) and [Zn(dmtz)F] (2a, 2b).
- Unusual network topologies (4.8(2), 4.12(2), (8,3)-b, 8(2).10-a) were observed.
- Framework 1b and 2a exhibit 1D nanotubular channels (hydrophilic and hydrophobic, respectively).
- Frameworks 2a and 2b show enhanced thermal stability compared to 1a and 1b.
- Selective sorption behavior was observed for 1b and 2a, correlating with pore properties.
Conclusions:
- Variations in reaction conditions lead to the formation of distinct supramolecular isomers with unique network structures.
- The coordination environment of zinc ions and the nature of the linker (formate vs. fluoride) significantly influence framework stability and pore characteristics.
- The synthesized frameworks, particularly 1b and 2a, demonstrate potential for selective guest molecule sorption.
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