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  4. Linear Polynuclear Helicates as a Link between Discrete Supramolecular Complexes and Programmed Infinite Polymetallic Chains
 
research article

Linear Polynuclear Helicates as a Link between Discrete Supramolecular Complexes and Programmed Infinite Polymetallic Chains

Dalla-Favera, Natalia
•
Hamacek, Josef
•
Borkovec, Michal
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2008
Chemistry - A European Journal

The contribution of the solvation energies to the assembly of polynuclear helicates reduces the free energy of intermetallic repulsion, DEMM, in condensed phase to such an extent that stable D3-symmetrical tetranuclear lanthanide-containing triplestranded helicates [Ln4(L4)3]12+ are quantitatively produced at millimolar concentrations, despite the twelve positive charge borne by these complexes. 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. Photophysical studies of [Eu4(L4)3]12+ confirm the existence of two different binding sites producing differentiated metal-centred emission at low temperature, which transforms into single site luminescence at room temperature because of intramolecular energy funelling processes

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Type
research article
DOI
10.1002/chem.200701465
Web of Science ID

WOS:000254872600006

Author(s)
Dalla-Favera, Natalia
Hamacek, Josef
Borkovec, Michal
Jeannerat, Damien
Gumy, Frédéric  
Bünzli, Jean-Claude G.  
Ercolani, Gianfranco
Piguet, Claude
Date Issued

2008

Published in
Chemistry - A European Journal
Volume

14

Issue

10

Start page

2994

End page

3005

Subjects

helical structures

•

multicomponent assembly

•

polynuclear

•

statistical factors

•

thermodynamics

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
LCSL  
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/20496
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