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Construction and Systematical Symmetric Studies of a Series of Supramolecular Clusters with Binary or Ternary Ammonium Triphenylacetates
Published on: February 15, 2016
Coordination-driven face-directed self-assembly of trigonal prisms. Face-based conformational chirality.
Douglas C Caskey1, Takuya Yamamoto, Chris Addicott
1Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado 80309-0215, USA.
Researchers created chiral trigonal prisms using platinum linkers and star connectors. Chirality transfer was observed, with distinct pyridine ring edge behaviors and temperature-dependent interconversion dynamics.
Area of Science:
- Supramolecular Chemistry
- Coordination Chemistry
- Materials Science
Background:
- Coordination-driven self-assembly is a powerful method for constructing complex molecular architectures.
- Trigonal prisms represent a fundamental polyhedral structure with potential applications in molecular recognition and catalysis.
Purpose of the Study:
- To synthesize and characterize novel trigonal prisms using a face-directed self-assembly approach.
- To investigate the influence of conformationally chiral star connectors on the resulting prism's chirality.
- To study the dynamic behavior of the pyridine ring edges within the assembled prisms.
Main Methods:
- Synthesis of four different trigonal prisms via coordination-driven self-assembly.
- Characterization using multinuclear and DOSY NMR, and dual ESI-FT-ICR mass spectrometry.
- Computational analysis using molecular mechanics.
- Kinetic studies via line-shape analysis and 1-D EXCHSY NMR for edge interconversion.
Main Results:
- High yields of four distinct trigonal prisms were achieved without template assistance.
- Chirality was successfully communicated from the star connector to the prism, demonstrating chirality transfer.
- NMR data confirmed distinct pyridine ring edges and revealed temperature-dependent interconversion dynamics.
- Two distinct activation energies for pyridine ring rotation were observed, suggesting complex dynamic behavior.
Conclusions:
- The face-directed self-assembly is an efficient route to complex chiral supramolecular structures.
- Conformationally chiral building blocks can induce chirality in polyhedral assemblies.
- The dynamic behavior of the prism edges is complex and exhibits temperature-dependent transitions.
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