Linear polynuclear helicates as a link between discrete supramolecular complexes and programmed infinite polymetallic chains

Dalla-Favera, Natalia; Hamacek, Joséf; Borkovec, Michal; Jeannerat, Damien; Gumy, Frédéric; Bünzli, Jean-Claude G.; Ercolani, Gianfranco; Piguet, Claude

doi:10.1002/chem.200701465

Scientific article

English

Linear polynuclear helicates as a link between discrete supramolecular complexes and programmed infinite polymetallic chains

Contributors

Dalla-Favera, Natalia; Hamacek, Joséf; Borkovec, Michal; Jeannerat, Damien; Gumy, Frédéric; Bünzli, Jean-Claude G.; Ercolani, Gianfranco; Piguet, Claude

Published in

Chemistry, vol. 14, no. 10, p. 2994-3005

Publication date

2008

Abstract

The contribution of the solvation energies to the assembly of polynuclear helicates reduces the free energy of intermetallic repulsion, EMM, in condensed phase to such an extent that stable D3-symmetrical tetranuclear lanthanide-containing triple-stranded 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.

UNIGE affiliation entities

Faculté des sciences / Section de chimie et biochimie / Département de chimie organique

Citation (ISO format)

DALLA-FAVERA, Natalia et al. Linear polynuclear helicates as a link between discrete supramolecular complexes and programmed infinite polymetallic chains. In: Chemistry, 2008, vol. 14, n° 10, p. 2994–3005. doi: 10.1002/chem.200701465

Article

Identifiers

PID : unige:7032
DOI : 10.1002/chem.200701465
PMID : 18293346

Journal ISSN

0947-6539

658views

0downloads

Creation

18/06/2010 08:55:23

First validation

18/06/2010 08:55:23

Update

14/10/2025 06:58:40

Status update

14/03/2023 15:42:19

Last indexation

01/09/2026 05:42:12

Linear polynuclear helicates as a link between discrete supramolecular complexes and programmed infinite polymetallic chains

Contributors

Published in

Publication date

Abstract

UNIGE affiliation entities

Citation (ISO format)

Main files (1)

Identifiers

Journal ISSN

Technical informations

Creation

First validation

Update

Status update

Last indexation