Understanding, controlling and programming cooperativity in self-assembled polynuclear complexes in solution.

@article{RiisJohannessen2009UnderstandingCA,
  title={Understanding, controlling and programming cooperativity in self-assembled polynuclear complexes in solution.},
  author={Thomas Riis-Johannessen and Natalia Dalla Favera and Tanya K Todorova and Stefan M Huber and Laura Gagliardi and Claude Piguet},
  journal={Chemistry},
  year={2009},
  volume={15 46},
  pages={
          12702-18
        }
}
Deviations from statistical binding, that is cooperativity, in self-assembled polynuclear complexes partly result from intermetallic interactions DeltaE(M,M), whose magnitudes in solution depend on a balance between electrostatic repulsion and solvation energies. These two factors have been reconciled in a simple point-charge model, which suggests severe and counter-intuitive deviations from predictions based solely on the Coulomb law when considering the variation of DeltaE(M,M) with metallic… Expand
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References

SHOWING 1-10 OF 86 REFERENCES
Linear polynuclear helicates as a link between discrete supramolecular complexes and programmed infinite polymetallic chains.
TLDR
A detailed modelling of the formation constants using statistical factors, adapted to self-assembly processes involving intra- and intermolecular connections, provides a set of five microscopic parameters which can be successfully used for rationalizing the stepwise generation of linear bi-, tri- and tetranuclear analogues. Expand
The origin of the surprising stabilities of highly charged self-assembled polymetallic complexes in solution.
TLDR
A judicious combination of Born-Haber cycles and the Born equation restores the expected electrostatic trend in the gas phase, in which intermetallic interactions can be simply modeled using a standard Coulombic approach. Expand
A simple thermodynamic model for quantitatively addressing cooperativity in multicomponent self-assembly processes--Part 2: Extension to multimetallic helicates possessing different binding sites.
TLDR
The extended site-binding model, which explicitly separates intramolecular interactions 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-stranding Eu(III) helicates. Expand
Self-Assembly of Tricuprous Double Helicates: Thermodynamics, Kinetics, and Mechanism
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, theExpand
A simple thermodynamic model for quantitatively addressing cooperativity in multicomponent self-assembly processes--part 1: Theoretical concepts and application to monometallic coordination complexes and bimetallic helicates possessing identical binding sites.
TLDR
A thermodynamic model has been developed for quantitatively estimating cooperativity in supramolecular polymetallic assemblies, and extension to the self-assembly of more sophisticated bimetallic helicates possessing identical binding sites is discussed. Expand
Assessment of cooperativity in self-assembly.
  • G. Ercolani
  • Medicine, Chemistry
  • Journal of the American Chemical Society
  • 2003
TLDR
The present method underscores the fact that positive cooperativity in artificial self-assembling systems is probably much more rare than it was previously thought. Expand
Effective concentration as a tool for quantitatively addressing preorganization in multicomponent assemblies: application to the selective complexation of lanthanide cations.
The beneficial entropic effect, which may be expected from the connection of three tridentate binding units to a strain-free covalent tripod for complexing nine-coordinate cations (Mz+ = Ca2+, La3+,Expand
A Model for Self-Assembly in Solution1
A model treating the competition, under thermodynamic control, between self-assembly and nonlinear random polymerization is presented. The fundamental quantities on which the treatment is based areExpand
Simple thermodynamics for unravelling sophisticated self-assembly processes.
TLDR
This Perspective focuses on the modelling of the free energy changes accompanying self-assembly processes and presents the original protein-ligand model borrowed from biology, which describes complicated multicomponent assemblies, and the extended site binding model, which is able to dissectfree energy changes occurring in sophisticated metal-ligands assemblies with a minimum set of microscopic parameters. Expand
How to adapt Scatchard plot for graphically addressing cooperativity in multicomponent self-assemblies.
TLDR
Applications to several polymetallic helicates reveal the presence of negatively cooperative processes attributed mainly to intermetallic repulsions, in agreement with recent thermodynamic models. Expand
...
1
2
3
4
5
...