Crystal chemistry and luminescence properties of tetrabutylphosphonium tetrakis(8-quinolinato)lanthanidate [P4444][Ln(Q)4]·2X (X = H2O and (CH3)2CO)Show others and affiliations
2025 (English)In: New Journal of Chemistry, ISSN 1144-0546, E-ISSN 1369-9261, Vol. 49, no 38, p. 16493-16500Article in journal (Refereed) Published
Abstract [en]
Since the discovery of AlQ3 (Q = 8-quinolinolato) quinolinato complexes, they have been extensively scrutinized as emitter materials for organic lighting. Herein, we report on the first representatives of a series of tetrabutylphosphonium tetrakis(8-quinolinolato)lanthanidate complexes [P4444][Ln(Q)4]·2X (Ln = Dy-Lu and Y; X = H2O for Ln = Dy-Tm, Lu and Y and (CH3)2CO for Ln = Yb), which are synthesised by a simple metathesis reaction of the respective potassium tetrakis(8-quinolinolato)lanthanidate salts with tetrabutylphosphonium bromide in acetone at room temperature. Single-crystal X-ray diffraction reveals that Ln(iii) is coordinated by four bidentate 8-quinolinato ligands in the form of a distorted square antiprism. The distinct [Ln(Q)4]− anions interact with the [P4444]+ cations through secondary bonding interactions, such as CH-π and van der Waals interactions, in addition to electrostatic coulombic interactions. Although these compounds contain crystal water/solvent molecules (and their synthesis does not require an inert atmosphere), they do not enter the metal coordination sphere but form pairwise intramolecular hydrogen bonds with the two 8-quinolinato ligands of the complex lanthanide anions. Combined differential scanning calorimetry-thermogravimetric analysis indicates that crystal water is lost at around 100 °C and [P4444][Ln(Q)4] is formed, which is stable up to 300 °C, where further degradation occurs. All compounds feature strong emission in the green region, originating from the π* → π transitions within the 8-quinolinato ligand, with lifetimes in the nanosecond range. The luminescence colour changes from blue-green to yellow-green depending on Ln3+, which opens up additional directions in the colour tuning of emitters for organic lighting applications.
Place, publisher, year, edition, pages
Royal Society of Chemistry, 2025. Vol. 49, no 38, p. 16493-16500
National Category
Inorganic Chemistry
Identifiers
URN: urn:nbn:se:umu:diva-245500DOI: 10.1039/d4nj03697bISI: 001563104900001Scopus ID: 2-s2.0-105017548147OAI: oai:DiVA.org:umu-245500DiVA, id: diva2:2007788
Funder
The Royal Swedish Academy of SciencesSwedish Energy Agency, 46676-1Swedish Research Council, 2019-02345Swedish Research Council, 2020-04437Swedish Foundation for Strategic ResearchSwedish Research Council, 2020-04437Novo Nordisk Foundation2025-10-212025-10-212025-10-21Bibliographically approved