Crystal structure and optical properties of a two-sited EuIII compound: an EuIII ion coordinated by two [EuIII(DOTA)]− complexes (DOTA is 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetate)
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Crystal structure and optical properties of a two-sited EuIII compound: an EuIII ion coordinated by two [EuIII(DOTA)]− complexes (DOTA is 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetate). / Thomsen, Maria Storm; Madsen, Anders Ø.; Sørensen, Thomas Just.
In: Acta Crystallographica Section C: Crystal Structure Communications, Vol. 77, No. 7, 01.07.2021, p. 354-364.Research output: Contribution to journal › Journal article › Research › peer-review
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T1 - Crystal structure and optical properties of a two-sited EuIII compound: an EuIII ion coordinated by two [EuIII(DOTA)]− complexes (DOTA is 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetate)
AU - Thomsen, Maria Storm
AU - Madsen, Anders Ø.
AU - Sørensen, Thomas Just
PY - 2021/7/1
Y1 - 2021/7/1
N2 - The structure and solid-state luminescence properties of an EuIII compound with two different lanthanide sites, [Eu(μ-O)5(OH)(H2O)2][Eu(DOTA)(H2O)]2 (DOTA is 1,4,7,10-tetrazacyclododecane-1,4,7,10-tetraacetate, C16H24N4O8), were determined. The compound crystallizes in a laminar structure in the triclinic space group P\overline{1}, where the two sites are a free europium(III) ion and an [Eu(DOTA)(H2O)]− complex. The crystal structure was determined using complex data treatment due to nonmerohedral twinning. Experimental data sets were recorded with large redundancy and separated according to scattering domains in order to obtain a reliable structure. In the first site, the [Eu(DOTA)(H2O)]− complex was found to adopt a capped twisted square-antiprismatic (cTSAP) conformation, where a capping water molecule increased the coordination number of the europium(III) site to nine (CN = 9). In the second site, the europium(III) ion was found to be coordinated by two water molecules, one hydroxide group and five oxide groups from neighbouring [Eu(DOTA)(H2O)]− complexes. The coordination geometry of this site was found to be a compressed square antiprism (SAP) and the coordination number of the europium(III) ion was found to be eight (CN = 8). A large increase in the rate constant of luminescence was observed for EuIII in [Eu(DOTA)(H2O)]− in solid-state luminescence spectroscopy measurements compared to in solution, which led to investigations of single crystals in deuterated media to exclude additional effects of quenching. We conclude that the most probable cause of the decrease in the observed luminescence lifetimes is the high asymmetry of the coordination environment of [Eu(DOTA)(D2O)]− in the [Eu(μ-O)5(OD)(D2O)2][Eu(DOTA)(D2O)]2 crystals.
AB - The structure and solid-state luminescence properties of an EuIII compound with two different lanthanide sites, [Eu(μ-O)5(OH)(H2O)2][Eu(DOTA)(H2O)]2 (DOTA is 1,4,7,10-tetrazacyclododecane-1,4,7,10-tetraacetate, C16H24N4O8), were determined. The compound crystallizes in a laminar structure in the triclinic space group P\overline{1}, where the two sites are a free europium(III) ion and an [Eu(DOTA)(H2O)]− complex. The crystal structure was determined using complex data treatment due to nonmerohedral twinning. Experimental data sets were recorded with large redundancy and separated according to scattering domains in order to obtain a reliable structure. In the first site, the [Eu(DOTA)(H2O)]− complex was found to adopt a capped twisted square-antiprismatic (cTSAP) conformation, where a capping water molecule increased the coordination number of the europium(III) site to nine (CN = 9). In the second site, the europium(III) ion was found to be coordinated by two water molecules, one hydroxide group and five oxide groups from neighbouring [Eu(DOTA)(H2O)]− complexes. The coordination geometry of this site was found to be a compressed square antiprism (SAP) and the coordination number of the europium(III) ion was found to be eight (CN = 8). A large increase in the rate constant of luminescence was observed for EuIII in [Eu(DOTA)(H2O)]− in solid-state luminescence spectroscopy measurements compared to in solution, which led to investigations of single crystals in deuterated media to exclude additional effects of quenching. We conclude that the most probable cause of the decrease in the observed luminescence lifetimes is the high asymmetry of the coordination environment of [Eu(DOTA)(D2O)]− in the [Eu(μ-O)5(OD)(D2O)2][Eu(DOTA)(D2O)]2 crystals.
U2 - 10.1107/S2053229621005647
DO - 10.1107/S2053229621005647
M3 - Journal article
C2 - 34216440
VL - 77
SP - 354
EP - 364
JO - Acta Crystallographica Section C: Crystal Structure Communications
JF - Acta Crystallographica Section C: Crystal Structure Communications
SN - 0108-2701
IS - 7
ER -
ID: 274475579