Mapping the distribution of electronic states within the 5D4 and 7F6 levels of Tb3+ complexes with optical spectroscopy
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Mapping the distribution of electronic states within the 5D4 and 7F6 levels of Tb3+ complexes with optical spectroscopy. / Kofod, Nicolaj; Henrichsen, Margrete Juel; Sørensen, Thomas Just.
I: Dalton Transactions, Bind 53, Nr. 10, 2024, s. 4461-4470.Publikation: Bidrag til tidsskrift › Tidsskriftartikel › Forskning › fagfællebedømt
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TY - JOUR
T1 - Mapping the distribution of electronic states within the 5D4 and 7F6 levels of Tb3+ complexes with optical spectroscopy
AU - Kofod, Nicolaj
AU - Henrichsen, Margrete Juel
AU - Sørensen, Thomas Just
PY - 2024
Y1 - 2024
N2 - The Tb(III) ion has the most intense luminescence of the trivalent lanthanide(III) ions. In contrast to Eu(III), where the two levels only include a single state, the high number of electronic states in the ground (7 F 6 ) and emitting ( 5 D4 ) levels makes detailed interpretations of the electronic structure—the crystal field— difficult. Here, luminescence emission and excitation spectra of Tb(III) complexes with 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA, [Tb(DOTA)(H2O)]−), ethylenediaminetetraacetic acid (EDTA, [Tb(EDTA)(H2 O)3]−) and diethylenetriaminepentaacetic acid (DTPA, [Tb(DTPA)(H2O)]2−) as well as the Tb(III) aqua ion ([Tb(H2 O)9 ] 3+ ) were recorded at room temperature and in frozen solution. Using these data the electronic structure of the 5 D4 multiplets of Tb(III) was mapped by considering the transitions to the singly degenerate 7 F0 state. A detailed spectroscopic investigation was performed and it was found that the 5 D4 multiplet could accurately be described as a single band for [Tb(H2 O)9 ]3+ , [Tb(DOTA)(H 2O)]− and [Tb (EDTA)(H 2O)3 ]−. In contrast, for [Tb(DTPA)(H2 O)]2− two bands were needed. These results demonstrated the ability of describing the electronic structure of the emitting 5 D4 multiplet using emission spectra. This offers an avenue for investigating the relationship between molecular structure and luminescent properties in detailed photophysical studies of Tb(III) ion complexes.
AB - The Tb(III) ion has the most intense luminescence of the trivalent lanthanide(III) ions. In contrast to Eu(III), where the two levels only include a single state, the high number of electronic states in the ground (7 F 6 ) and emitting ( 5 D4 ) levels makes detailed interpretations of the electronic structure—the crystal field— difficult. Here, luminescence emission and excitation spectra of Tb(III) complexes with 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA, [Tb(DOTA)(H2O)]−), ethylenediaminetetraacetic acid (EDTA, [Tb(EDTA)(H2 O)3]−) and diethylenetriaminepentaacetic acid (DTPA, [Tb(DTPA)(H2O)]2−) as well as the Tb(III) aqua ion ([Tb(H2 O)9 ] 3+ ) were recorded at room temperature and in frozen solution. Using these data the electronic structure of the 5 D4 multiplets of Tb(III) was mapped by considering the transitions to the singly degenerate 7 F0 state. A detailed spectroscopic investigation was performed and it was found that the 5 D4 multiplet could accurately be described as a single band for [Tb(H2 O)9 ]3+ , [Tb(DOTA)(H 2O)]− and [Tb (EDTA)(H 2O)3 ]−. In contrast, for [Tb(DTPA)(H2 O)]2− two bands were needed. These results demonstrated the ability of describing the electronic structure of the emitting 5 D4 multiplet using emission spectra. This offers an avenue for investigating the relationship between molecular structure and luminescent properties in detailed photophysical studies of Tb(III) ion complexes.
U2 - 10.1039/D3DT03657J
DO - 10.1039/D3DT03657J
M3 - Journal article
VL - 53
SP - 4461
EP - 4470
JO - Dalton Transactions (Online)
JF - Dalton Transactions (Online)
SN - 1477-9234
IS - 10
ER -
ID: 384571353