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Switchable Metal-Ion Selectivity in Sulfur-Functionalised Pillar[5]arenes and Their Host-Guest Complexes
Bunyaporn Todee1, Patharaporn Sanae1, Araya Ruengsuk1
1Department of Chemistry and Center of Excellence for Innovation in Chemistry (PERCH-CIC), Faculty of Sciense, Mahidol University, Bangkok, 10400, Thailand.
Chemistry, an Asian Journal
|November 16, 2023
Summary
New sulfur-functionalized pillar[5]arenes self-assemble and bind guests. These macrocycles show potential for metal ion sensing and extraction, with pseudorotaxanes enhancing performance.
Area of Science:
- Supramolecular Chemistry
- Macrocyclic Chemistry
- Materials Science
Background:
- Pillar[5]arenes are macrocyclic compounds with tunable properties.
- Functionalization of pillararenes can lead to novel host-guest chemistry and material applications.
Purpose of the Study:
- To synthesize and characterize novel sulfur-functionalized pillar[5]arenes.
- To investigate their self-assembly behavior in solution and solid states.
- To explore their host-guest complexation, metal ion binding, and sensing capabilities.
Main Methods:
- Nucleophilic substitution reactions for synthesis.
- Dynamic Light Scattering (DLS) and Scanning Electron Microscopy (SEM) for assembly studies.
- X-ray crystallography for solid-state structure determination.
- Nuclear Magnetic Resonance (NMR) and fluorescence spectroscopy for binding studies.
- Host-guest complexation with dinitrile guests.
- Liquid-liquid extraction for metal ion transfer.
Main Results:
- Successful synthesis of sulfur-functionalized pillar[5]arenes.
- Pillararene macrocycles exhibit self-assembly in acetonitrile and solvent-dependent assembly in the solid state.
- Sulfur substituents influence organic guest encapsulation and metal ion binding (S-M2+ coordination).
- Formation of pseudorotaxane host-guest complexes observed.
- Fluorescence quenching by Hg2+ and Cu2+; pseudorotaxanes improve selectivity and sensitivity.
- Macrocycles facilitate Cu2+ transfer from aqueous to organic phases.
Conclusions:
- Sulfur-functionalized pillar[5]arenes are versatile macrocycles with tunable binding properties.
- Self-assembly behavior is dependent on the macrocycle structure and environment.
- These compounds show promise as sensors for metal ions and in extraction applications.
- Pseudorotaxane formation can enhance sensing performance.
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