Stoichiometry of lanthanide(<scp>iii</scp>) complexes with tripodal aminophosphonic ligands – a new solution to an old problem

Janicki, Rafał; Gałęzowska, Joanna; Mondry, Anna

doi:10.1039/c7qi00191f

Cited by 9 publications

(1 citation statement)

References 63 publications

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“…In consequence the analysis of luminescence spectra of lanthanide ions in solution should be carried out very carefully, because the temperature changes in luminescence intensity for some cases, may be caused by physical changes of solution only, and not necessarily by a chemical reaction ‐ for instance by hydration equilibrium. Coincidentally, the existence of hydration equlibria in solution is often observed for the case of highly luminescent lanthanide cations from the middle of the series namely: Eu(III), Gd(III), Tb(III), and normalisation of luminescence spectra, indispensable for quantitative speciation analysis of solution,,, is possible for the case of Eu(III), only.…”

Section: Resultsmentioning

confidence: 99%

Experimental and Ab Initio Study on the Intensitiesof f–f Transitions for the Molecular Eu(III)‐DOTP System

2019

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The experimental f-f transition intensities, derived from UV-vis absorption and emission spectra of Eu(III)-DOTP systems (where DOTP is 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetrayl)tetrakis-(methylene))-tetraphosphonate anion) in [C(NH 2 ) 3 ] 5 [Eu(DOTP)] ⋅12.5H 2 O and K 5 [Eu(DOTP)]⋅11H 2 O crystals and in solution, were analyzed in terms of Judd-Ofelt theory. A non standard approach was used to calculate Ω λ parameters by including both the absorption 7 F 0 ! 2S + 1 L J and emission 5 D 0 ! 7 F J bands in the calculation procedure. The f-f transition intensities of two {K 4 [Eu(DOTP)]}clusters representing the two different forms of Eu(III)-DOTP complex in K 5 [Eu(DOTP)]⋅11H 2 O crystal, calculated within ab initio approach were compared with the experimental counterparts. The theoretical results provided a deeper insight into the nature of the hypersensitive and highly-forbidden f-f transitions for system under study. The possible improvements of the theoretical approach are discussed in the light of the known mechanisms contributing to the intensities of f-f transitions. Finally the solution structure of the [Eu (DOTP)] 5complex was examined by complementary techniques including temperature dependent UV-vis absorption and time-resolved emission spectroscopy. This enabled us to show that the structure of the [Eu(DOTP)] 5complex in solution is practically the same as those in crystals. In particular it means that there are no water molecules coordinated to the central Eu(III) cation. The observed decrease of luminescence integral intensities of the 5 D 0 ! 7 F J bands at elevated temperatures of solution, usually assigned to a chemical reaction, is brought about actually by the changes of solution viscosity.[a] Dr.

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Section: Resultsmentioning

confidence: 99%

Experimental and Ab Initio Study on the Intensitiesof f–f Transitions for the Molecular Eu(III)‐DOTP System

2019

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Magnetite nanoparticles with aminomethylenephosphonic groups: synthesis, characterization and uptake of europium(III) ions from aqueous media

et al. 2019

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Electrochemical Ce3+/Ce4+ and Eu2+/Eu3+ interconversion, complexation, and electrochemical CO2 reduction on thio-terpyridyl-derivatized Au electrodes

Park

Joo

Maeng

et al. 2022

Applied Surface Science

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Stoichiometry of lanthanide(iii) complexes with tripodal aminophosphonic ligands – a new solution to an old problem

Abstract: The [Eu(NP2py)2]5− complex crystallized as a [C(NH2)3]5[Eu(NP2py)2]·12 compound. However, the formation of the [Ln(NP2py)2]5– species in aqueous solution starts at pH as high as 8.

Cited by 9 publications

References 63 publications

Experimental and Ab Initio Study on the Intensitiesof f–f Transitions for the Molecular Eu(III)‐DOTP System

Experimental and Ab Initio Study on the Intensitiesof f–f Transitions for the Molecular Eu(III)‐DOTP System

Magnetite nanoparticles with aminomethylenephosphonic groups: synthesis, characterization and uptake of europium(III) ions from aqueous media

Electrochemical Ce3+/Ce4+ and Eu2+/Eu3+ interconversion, complexation, and electrochemical CO2 reduction on thio-terpyridyl-derivatized Au electrodes

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