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A Simple Thermodynamic Model for Quantitatively Addressing Cooperativity in Multicomponent Self‐Assembly Processes—Part 2: Extension to Multimetallic Helicates Possessing Different Binding Sites
Author(s) -
Hamacek Josef,
Borkovec Michal,
Piguet Claude
Publication year - 2005
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200500289
Subject(s) - cooperativity , intramolecular force , cooperative binding , chemistry , supramolecular chemistry , extension (predicate logic) , intermetallic , simple (philosophy) , metal , crystallography , computational chemistry , binding site , stereochemistry , combinatorial chemistry , crystal structure , computer science , organic chemistry , biochemistry , programming language , philosophy , alloy , epistemology
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.