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Title: Investigating subtle 4f vs. 5f coordination differences using kinetically inert Eu(III), Tb(III), and Cm(III) complexes of a coumarin-appended 1,4,7,10-tetraazacyclododecane-1,4,7-triacetate (DO3A) ligand

Abstract

In this paper, in order to reveal subtle differences between the solution chemistries of trivalent 4f and 5f elements, the physicochemical and photophysical properties of europium(III), terbium(III) and curium(III) complexes formed with a 7-methoxy-coumarin appended 1,4,7,10-tetraazadodecane-1,4,7-triacid (DO3A) ligand were studied. All three complexes were found to be kinetically inert and exhibit stability constants similar to their 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) equivalents. The Cm(III) and Eu(III) complexes feature strong sensitised emission, while the triplet energy of the coumarin prohibits efficient sensitisation of the Tb(III) analogue. The data presented here indicate significant differences in perturbation of the sensitising chromophore photophysics between the 4f and 5f elements. Finally, in contrast, the size of the metal center appears to not be a determining factor for the physicochemical properties of these kinetically inert Eu(III), Tb(III), and Cm(III) complexes.

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [1]
  1. Univ. of Copenhagen (Denmark). Nano-Science Center. Dept. of Chemistry
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division; Univ. of California, Berkeley, CA (United States). Dept. of Nuclear Engineering
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); Knud Højgaards Fond (Denmark); Oticon Fonden (Denmark); Lundbeck Foundation (Denmark); Villum Foundation (Denmark); Carlsberg Foundation (Denmark); Univ. of Copenhagen (Denmark)
OSTI Identifier:
1458506
Alternate Identifier(s):
OSTI ID: 1437673
Grant/Contract Number:  
AC02-05CH11231; 14922
Resource Type:
Accepted Manuscript
Journal Name:
Dalton Transactions
Additional Journal Information:
Journal Volume: 47; Journal Issue: 21; Journal ID: ISSN 1477-9226
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Junker, Anne Kathrine R., Deblonde, Gauthier J. -P., Abergel, Rebecca J., and Sorensen, Thomas Just. Investigating subtle 4f vs. 5f coordination differences using kinetically inert Eu(III), Tb(III), and Cm(III) complexes of a coumarin-appended 1,4,7,10-tetraazacyclododecane-1,4,7-triacetate (DO3A) ligand. United States: N. p., 2018. Web. doi:10.1039/c8dt01547c.
Junker, Anne Kathrine R., Deblonde, Gauthier J. -P., Abergel, Rebecca J., & Sorensen, Thomas Just. Investigating subtle 4f vs. 5f coordination differences using kinetically inert Eu(III), Tb(III), and Cm(III) complexes of a coumarin-appended 1,4,7,10-tetraazacyclododecane-1,4,7-triacetate (DO3A) ligand. United States. doi:10.1039/c8dt01547c.
Junker, Anne Kathrine R., Deblonde, Gauthier J. -P., Abergel, Rebecca J., and Sorensen, Thomas Just. Wed . "Investigating subtle 4f vs. 5f coordination differences using kinetically inert Eu(III), Tb(III), and Cm(III) complexes of a coumarin-appended 1,4,7,10-tetraazacyclododecane-1,4,7-triacetate (DO3A) ligand". United States. doi:10.1039/c8dt01547c. https://www.osti.gov/servlets/purl/1458506.
@article{osti_1458506,
title = {Investigating subtle 4f vs. 5f coordination differences using kinetically inert Eu(III), Tb(III), and Cm(III) complexes of a coumarin-appended 1,4,7,10-tetraazacyclododecane-1,4,7-triacetate (DO3A) ligand},
author = {Junker, Anne Kathrine R. and Deblonde, Gauthier J. -P. and Abergel, Rebecca J. and Sorensen, Thomas Just},
abstractNote = {In this paper, in order to reveal subtle differences between the solution chemistries of trivalent 4f and 5f elements, the physicochemical and photophysical properties of europium(III), terbium(III) and curium(III) complexes formed with a 7-methoxy-coumarin appended 1,4,7,10-tetraazadodecane-1,4,7-triacid (DO3A) ligand were studied. All three complexes were found to be kinetically inert and exhibit stability constants similar to their 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) equivalents. The Cm(III) and Eu(III) complexes feature strong sensitised emission, while the triplet energy of the coumarin prohibits efficient sensitisation of the Tb(III) analogue. The data presented here indicate significant differences in perturbation of the sensitising chromophore photophysics between the 4f and 5f elements. Finally, in contrast, the size of the metal center appears to not be a determining factor for the physicochemical properties of these kinetically inert Eu(III), Tb(III), and Cm(III) complexes.},
doi = {10.1039/c8dt01547c},
journal = {Dalton Transactions},
number = 21,
volume = 47,
place = {United States},
year = {2018},
month = {5}
}

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Figures / Tables:

Figure 1 Figure 1: Molecular structure of the investigated complexes M.L and the equilibrium between a hepta- and octadentate binding mode (A), a scaled representation of the ionic radius of Eu(III), Tb(III), and Cm(III) ions (B),36 an illustration of the difference in radial expansion 4ƒ (inside ionic radius) and 5ƒ (extends beyondmore » ionic radius) orbitals (C), and a schematic representation of the antenna principle (D).« less

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