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Self‐Assembly of Tricuprous Double Helicates: Thermodynamics, Kinetics, and Mechanism
Author(s) -
FatinRouge Nicolas,
Blanc Sylvie,
Pfeil Armin,
Rigault Annie,
AlbrechtGary AnneMarie,
Lehn JeanMarie
Publication year - 2001
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/1522-2675(20010613)84:6<1694::aid-hlca1694>3.0.co;2-t
Subject(s) - chemistry , cooperativity , kinetics , cooperative binding , kinetic energy , stereochemistry , crystallography , chemical stability , binding site , organic chemistry , physics , quantum mechanics , biochemistry
We report in this paper the coordination and kinetic properties of two oligobipyridine strands, which contain three 2,2′‐bipyridine subunits separated by oxydimethylene bridges, the 4,4′‐bis(CONET 2 )‐substituted L and the 4,4′‐bis(CO 2 Et)‐substituted L ′. Spectrophotometric measurements allowed the characterization of thermodynamic complexes and kinetic intermediates* which are involved in the self‐assembly process of L 2 Cu 3 and L Cu 3 helicates. The reaction presents positive cooperativity for the binding of two 2,2′‐bipyridine strands to the cuprous cations. While reactive kinetic intermediates* present distorted coordination geometries around Cu I , the final rearrangement of the tricuprous bistranded helicates allows more closely tetrahedral coordination of each cation and reduces the interactions. Differences in the bulkiness and electronic properties of the L and L ′ substituents do not affect significantly the stability of the corresponding helicates, but greatly influence binding rates in the self‐assembly process.