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Complementarity and Preorganization


  1. James B. Wittenberg,
  2. Lyle Isaacs

Published Online: 15 MAR 2012

DOI: 10.1002/9780470661345.smc004

Supramolecular Chemistry: From Molecules to Nanomaterials

Supramolecular Chemistry: From Molecules to Nanomaterials

How to Cite

Wittenberg, J. B. and Isaacs, L. 2012. Complementarity and Preorganization. Supramolecular Chemistry: From Molecules to Nanomaterials. .

Author Information

  1. University of Maryland, College Park, MD, USA

Publication History

  1. Published Online: 15 MAR 2012


The principle of complementarity states that “to complex, hosts must have binding sites which can simultaneously contact and attract the binding sites of the guests without generating internal strains or strong nonbonded repulsions.” The principle of preorganization states that “the more highly hosts and guests are organized for binding and low solvation prior to their complexation, the more stable will be their complexes.” This chapter presents examples of classical and contemporary systems that exemplify different aspects of these two principles which are cornerstones of the discipline of supramolecular chemistry. The final sections of the chapter discuss situations (e.g., chemical sensing arrays and dynamic combinatorial chemistry) where adhering to the principle of preorganization may be detrimental to the function of the system.


  • complementarity;
  • preorganization;
  • hydrogen bonds;
  • host–guest complex;
  • secondary interactions;
  • predisposition