A Simple Thermodynamic Model for Quantitatively Addressing Cooperativity in Multicomponent Self-Assembly Processes—Part 2: Extension to Multimetallic Helicates Possessing Different Binding Sites - Archive ouverte HAL Access content directly
Journal Articles Chemistry - A European Journal Year : 2005

A Simple Thermodynamic Model for Quantitatively Addressing Cooperativity in Multicomponent Self-Assembly Processes—Part 2: Extension to Multimetallic Helicates Possessing Different Binding Sites

Abstract

The extended site-binding model, which explicitly separates intramolecular interactions (i.e., intermetallic and interligand) from the successive binding of metal ions to polytopic receptors, is used for unravelling the self-assembly of trimetallic double-stranded Cu(I) and triple-stranded Eu(III) helicates. A thorough analysis of the available stability constants systematically shows that negatively cooperative processes operate, in strong contrast with previous reports invoking either statistical behaviours or positive cooperativity. Our results also highlight the need for combining successive generations of complexes with common binding units, but with increasing metallic nuclearities, for rationalizing and programming multicomponent supramolecular assemblies.

Dates and versions

hal-02122627 , version 1 (07-05-2019)

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Josef Hamacek, Michal Borkovec, Claude Piguet. A Simple Thermodynamic Model for Quantitatively Addressing Cooperativity in Multicomponent Self-Assembly Processes—Part 2: Extension to Multimetallic Helicates Possessing Different Binding Sites. Chemistry - A European Journal, 2005, 11 (18), pp.5227-5237. ⟨10.1002/chem.200500289⟩. ⟨hal-02122627⟩
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