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Keywords:

  • Complex formation;
  • Host–guest chemistry;
  • Cyclophanes;
  • Molecular recognition;
  • Macrocycles

Abstract

Since the discovery of the crown ethers by Pedersen twenty years ago, the chemistry of synthetic hosts for the selective complexation of organic and inorganic guests has seen an extraordinarily rapid development. This article discusses in particular the contributions provided by synthetic cyclophanes as hosts to the understanding of molecular complexation of neutral organic guest molecules in aqueous and organic solvents. In aqueous solution, cyclophanes form stoichiometric complexes with neutral aromatic guests which can approach enzyme-substrate complexes in their stability. Efficient molecular complexation is also observed in organic environments. Here, as a result of large solvation effects, the strength of complexation is strongly dependent on the nature of the organic solvent. Electron donor-acceptor interactions can contribute significantly to the stability of complexes formed between cyclophane hosts and aromatic guests. Force-field calculations together with computer graphics are powerful tools in the design of water-soluble, optically active hosts for chiral recognition of complexed racemic guests. Simple and selective functionalization of the cyclophane framework leads to stable, bioorganic catalysts. Like enzymes, these catalysts bind their substrates in a rapid equilibrium prior to the reaction steps. As a perspective, some fascinating research objectives in the field of molecular recognition and catalysis which can be targeted with designed cyclophane hosts are shown.