Jump to main content
Jump to site search

Issue 34, 2013
Previous Article Next Article

A TRLFS study on the complexation of novel BTP type ligands with Cm(iii)

Author affiliations

Abstract

Two BTP-type N-donor ligands with different numbers of aromatic nitrogen atoms (2,6-bis(4-ethyl-pyridazin-1-yl)pyridine, Et-BDP and 2,6-bis(4-npropyl-2,3,5,6-tetrazine-1-yl)pyridine, nPr-Tetrazine) have been synthesized and characterized by NMR and MS techniques. The complexation with Cm(III) in 2-propanol–water (1 : 1, vol.) is studied for both ligands using time resolved laser-induced fluorescence spectroscopy (TRLFS) and the complexation properties are compared to nPr-BTP. With increasing the ligand concentration three different species, the 1 : 1-, 1 : 2- and 1 : 3-complex, were found. Log β3 values of 7.6 for the formation of Cm(Et-BDP)3 and 9.2 for the formation of Cm(nPr-Tetrazine)3 are determined. The complexation with nPr-Tetrazine shows slow kinetics. Thermodynamic data of the complexation reactions are determined in a temperature range of 25 °C–60 °C. The complexation with Et-BDP is exothermic (ΔH = −16.3 ± 1.2 kJ mol−1) and exergonic (ΔG = −43.8 ± 2.6 kJ mol−1) whereas the complexation with nPr-Tetrazine is endothermic (ΔH = 43.9 ± 3.1 kJ mol−1) and exergonic (ΔG = −51.7 ± 2.2 kJ mol−1). In the case of the latter the complexation is driven by a highly positive reaction entropy change (ΔS = 320.6 ± 15.4 J mol−1 K−1). In comparison to nPr-BTP, less negative ΔG values were found for the complexation of Cm(III) with both ligands.

Graphical abstract: A TRLFS study on the complexation of novel BTP type ligands with Cm(iii)

Back to tab navigation

Supplementary files

Publication details

The article was received on 27 Feb 2013, accepted on 22 Mar 2013 and first published on 25 Mar 2013


Article type: Paper
DOI: 10.1039/C3DT50536G
Dalton Trans., 2013,42, 12139-12147

  •   Request permissions

    A TRLFS study on the complexation of novel BTP type ligands with Cm(III)

    B. B. Beele, E. Rüdiger, F. Schwörer, U. Müllich, A. Geist and P. J. Panak, Dalton Trans., 2013, 42, 12139
    DOI: 10.1039/C3DT50536G

Search articles by author

Spotlight

Advertisements