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Nanosized polymetallic resorcinarene-based host assemblies that strongly bind fullerenes
O Danny Fox1, James Cookson, Emma J S Wilkinson
1Department of Chemistry, University of Oxford, Inorganic Chemistry Laboratory, South Parks Road, Oxford, OX1 3QR, U.K.
Journal of the American Chemical Society
|May 25, 2006
Summary
Researchers created polymetallic nanostructures using metal-directed assembly. These structures effectively bind fullerenes (C60 and C70) through dithiocarbamate interactions, forming cage-like or loop architectures.
Area of Science:
- Supramolecular Chemistry
- Nanomaterials Science
- Coordination Chemistry
Background:
- Cavitands are versatile hosts capable of forming complex assemblies.
- Dithiocarbamate ligands offer unique coordination properties with transition metals.
- Fullerenes are important carbon allotropes with diverse applications.
Purpose of the Study:
- To synthesize polymetallic nanodimensional assemblies using dithiocarbamate-functionalized cavitands.
- To investigate the influence of metal coordination geometry on the resulting architectures.
- To explore the binding interactions between these assemblies and fullerenes (C60 and C70).
Main Methods:
- Metal-directed assembly of dithiocarbamate-functionalized cavitands with late transition metals (Ni, Pd, Cu, Au, Zn, Cd).
- X-ray crystallography to determine complex structures (octanuclear cages, hexanuclear loops).
- Spectroscopic (UV-Vis, NMR), electrochemical methods, electrospray mass spectrometry, and molecular modeling to study fullerene binding.
Main Results:
- Formation of "cagelike" octanuclear complexes with square planar metal centers and "molecular loop" hexanuclear structures with square-based pyramidal metal geometries.
- Demonstration of steric and electronic complementarity between the host assemblies and fullerenes.
- Strong binding of fullerenes via dithiocarbamate sulfur atoms, with evidence of encapsulation in copper(II) complexes due to ligand lability.
Conclusions:
- Metal coordination geometry is a critical determinant of polymetallic assembly architecture.
- Dithiocarbamate-cavitand frameworks provide effective binding sites for fullerenes.
- The dynamic nature of metal-dithiocarbamate bonds can facilitate guest encapsulation.
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