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Terazzi E, Guénée L, Bocquet B, et al. A simple chemical tuning of the effective concentration: selection of single-, double-, and triple-stranded binuclear lanthanide helicates. Chemistry. 2009;15(46):12719-32doi: 10.1002/chem.200902026.
Terazzi, E., Guénée, L., Bocquet, B., Lemonnier, J. F., Dalla Favera, N., & Piguet, C. (2009). A simple chemical tuning of the effective concentration: selection of single-, double-, and triple-stranded binuclear lanthanide helicates. Chemistry (Weinheim an der Bergstrasse, Germany), 15(46), 12719-32. https://doi.org/10.1002/chem.200902026
Terazzi, Emmanuel, et al. "A simple chemical tuning of the effective concentration: selection of single-, double-, and triple-stranded binuclear lanthanide helicates." Chemistry (Weinheim an der Bergstrasse, Germany) vol. 15,46 (2009): 12719-32. doi: https://doi.org/10.1002/chem.200902026
Terazzi E, Guénée L, Bocquet B, Lemonnier JF, Dalla Favera N, Piguet C. A simple chemical tuning of the effective concentration: selection of single-, double-, and triple-stranded binuclear lanthanide helicates. Chemistry. 2009 Nov 23;15(46):12719-32. doi: 10.1002/chem.200902026. PMID: 19784971.
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Chemistry. 2009 Nov 23;15(46):12719-32. doi: 10.1002/chem.200902026.

A simple chemical tuning of the effective concentration: selection of single-, double-, and triple-stranded binuclear lanthanide helicates.

Chemistry (Weinheim an der Bergstrasse, Germany)

Emmanuel Terazzi, Laure Guénée, Bernard Bocquet, Jean-François Lemonnier, Natalia Dalla Favera, Claude Piguet

Affiliations

  1. Department of Inorganic, Analytical and Applied Chemistry, University of Geneva, 30 quai E. Ansermet, 1211 Geneva 4, Switzerland. [email protected]

PMID: 19784971 DOI: 10.1002/chem.200902026

Abstract

The replacement of terminal 2-benzimidazol-6-carboxypyridine (two internal rotational degrees of freedom) with 2-benzimidazol-8-hydroxyquinoline (one internal rotational degree of freedom) into segmental bis-tridentate ligands in going from L2 and [L3-2 H](2-) to [L12 b-2 H](2-) does not significantly affect the structures of the resulting binuclear lanthanide triple-stranded helical complexes [Ln(2)(L2)(3)](6+), [Ln(2)(L3-2 H)(3)], and [Ln(2)(L12 b-2 H)(3)] (palindromic helices, intermetallic contact distance approximately 9 A, helical pitch approximately 1.4 nm per turn). However, their thermodynamic assemblies are completely different in solution, as evidenced by the spectacular decrease of the effective concentrations by two orders of magnitude for [L12 b-2 H](2-). This key parameter in the [Ln(2)(L12 b-2 H)(n)] (n=2, 3) complexes is further abruptly modulated along the lanthanide series (Ln=La to Lu), which provides an unprecedented tool for 1) tuning the number of ligand strands in the final helicates, 2) selectively coordinating lanthanides in the various complexes, and 3) controlling the ratio of lanthanide-containing polymers over discrete assemblies.

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