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A calix[4]arene carceplex with four Rh2 4+ fasteners.
F Albert Cotton1, Peng Lei, Chun Lin
1Laboratory for Molecular Structure and Bonding, Department of Chemistry, P.O. Box 30012, Texas A&M University, College Station, Texas 77842-3012, USA. cotton@tamu.edu
Journal of the American Chemical Society
|February 5, 2004
Summary
Researchers assembled stable spheroidal carceplexes by linking calix[4]arenes with dimetal units, trapping molecules or ions. These cages exhibit remarkable stability and allow for in-crystal ligand exchange, demonstrating dynamic host-guest chemistry.
Area of Science:
- Supramolecular Chemistry
- Coordination Chemistry
- Materials Science
Background:
- Development of molecular cages for guest encapsulation.
- Utilizing calix[4]arenes as building blocks for complex architectures.
- Exploring metal-metal bonded units in supramolecular assemblies.
Purpose of the Study:
- To synthesize and characterize novel spheroidal carceplexes.
- To investigate the encapsulation of molecular and ionic guests.
- To evaluate the stability and dynamic properties of the carceplexes.
Main Methods:
- Assembly of carceplexes by linking calix[4]arenes with dirhodium units.
- Characterization using X-ray crystallography, NMR, IR, and mass spectrometry.
- Investigation of axial ligand exchange in single crystals.
Main Results:
- Successful synthesis of a tetraethylammonium carceplex (1b) with trapped tetraethylammonium ion.
- Demonstration of high stability and dynamic axial ligand exchange (acetonitrile/water) without loss of crystallinity.
- Characterization of related dimetal-calixarene compounds with dirhodium and dimolybdenum units.
Conclusions:
- Spheroidal carceplexes can be robustly constructed from calix[4]arenes and dimetal units.
- The carceplexes exhibit significant stability and tunable guest environments.
- In-crystal ligand exchange highlights the potential for dynamic supramolecular materials.