Issue 41, 2022

Invisible strings. The first single crystal of the cTSAP form of [Eu(DOTA)(H2O)] has an electronic structure similar to one of the reported cSAP forms

Abstract

The coordination geometry of lanthanide(III) ions is extremely sensitive to perturbation from the surrounding environment. Changes in the crystal field can be observed as spectral variations in the emission spectra of luminescent lanthanide(III) ions. Europium(III) ions are commonly used to correlate luminescence properties to the crystal field. In solution, kinetically inert complexes as [Ln(DOTA)(H2O)] can fluctuate and give rise to different diastereomers (H4DOTA = 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid). The [Ln(DOTA)(H2O)] complex adopts a capped square antiprism (cSAP) geometry but can rotate into a capped twisted square antiprism (cTSAP). The time scale of the solution dynamics in [Ln(DOTA)(H2O)] is shorter than that of luminescence emission, thus, structural averages are observed in the emission spectra. For the first time, we were able to crystallise both forms of the [Eu(DOTA)(H2O)] diastereomers. The single crystal structure was combined with single crystal luminescence spectroscopy to reveal the electronic structure of Eu(III) in each form of the complex. The coordination geometry of the crystallized cSAP and cTSAP forms of the complex was compared to ideal coordination polyhedra using a continuous symmetry measure in the AlignIt code. The diastereomers of [Eu(DOTA)(H2O)] all demonstrate very little deviation from ideal geometries yet nearly identical electronic properties were observed from the two different forms.

Graphical abstract: Invisible strings. The first single crystal of the cTSAP form of [Eu(DOTA)(H2O)]− has an electronic structure similar to one of the reported cSAP forms

Supplementary files

Article information

Article type
Paper
Submitted
11 Eost 2022
Accepted
25 Gwen. 2022
First published
30 Gwen. 2022

Dalton Trans., 2022,51, 15725-15733

Invisible strings. The first single crystal of the cTSAP form of [Eu(DOTA)(H2O)] has an electronic structure similar to one of the reported cSAP forms

M. Storm Thomsen, S. Parsons and T. J. Sørensen, Dalton Trans., 2022, 51, 15725 DOI: 10.1039/D2DT02633C

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