Chapter Two

Thermodynamic Effective Molarities for Supramolecular Complexes

P. Motloch and C.A. Hunter1     University of Cambridge, Cambridge, United Kingdom1 Corresponding author: E-mail: 


Kinetic effective molarities (EM) that quantify the increase in reaction rate for intramolecular formation of covalent bonds compared with the corresponding intermolecular process often have physically impossible values (up to 1013 M). It is therefore widely assumed that multivalent supramolecular systems could attain similarly large values of thermodynamic EM for formation of cooperative intramolecular noncovalent interactions. However, a survey of the literature shows that this is the exception rather than the rule. ...

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