Anhydrous, Homoleptic Lanthanide Frameworks with the Pentafluoroethyltricyanoborate Anion.
Pentafluoroethyltricyanoborate frameworks of rare-earth metal ions of the general formula [Ln{C2F5B(CN)3}3(OH2)n] (Ln = La, Eu, Ho; n = 0, 3; [Ln13(OH2)n]) were synthesized using the oxonium salt (H3O)[C2F5B(CN)3] ((H3O)1) and lanthanide chlorides LnCl3·nH2O as starting compounds. Single-crystals of∞3[La{C2F5B(CN)3}3] (∞3[La13]) are obtained from the room temperature ionic liquid (RTIL) [EMIm]1 using either a ionothermal approach or by recrystallization of anhydrous microcrystalline [La13] that is obtained from reactions in aqueous media after drying in a vacuum. Removal of water from [Ln13(OH2)3] (Ln = Eu, Ho) to give microcrystalline∞3[Ln13] is achieved in a vacuum at elevated temperatures. All compounds were characterized by vibrational and NMR spectroscopy, thermogravimetry, and elemental analysis. The structures of the three-dimensional coordination polymers∞3[Eu13(OH2)3] and∞3[La13] were elucidated by single-crystal X-ray-diffraction. According to powder diffraction studies on anhydrous∞3[Ln13] (Ln = La, Eu, Ho), the three compounds are isotypic. A study of the photoluminescence properties reveals that both Eu3+compounds, [Eu13] and [Eu13(OH2)3], are strongly luminescent, the emission of the anhydrous framework being significantly more intense than the one of the hydrate. The Eu-compounds benefit from a sensitizer effect of the anion. In contrast, the Ho-containing framework∞3[Ho13] exhibits separate chromophores and a strong reabsorption of the fluorescence by the Ho3+ions.
Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg , Am Hubland, 97074 Würzburg, Germany.
Tatjana
T
Ribbeck
Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg , Am Hubland, 97074 Würzburg, Germany.
Sven H
SH
Zottnick
Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg , Am Hubland, 97074 Würzburg, Germany.
Christoph
C
Kerpen
Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg , Am Hubland, 97074 Würzburg, Germany.
Johannes
J
Landmann
Dr. Ignatiev-Chemistry Consultancy , 47058 Duisburg, Germany.
Nikolai V
NV
Ignat'ev
Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg , Am Hubland, 97074 Würzburg, Germany.
Klaus
K
Müller-Buschbaum
Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg , Am Hubland, 97074 Würzburg, Germany.|Institut für nachhaltige Chemie & Katalyse mit Bor (ICB), Julius-Maximilians-Universität Würzburg , Am Hubland, 97074 Würzburg, Germany.
Maik
http://orcid.org/0000-0002-6098-7148
M
Finze