Nano‐Nonanuclear Mixed‐Lanthanide Clusters [Eu_9–xTb_x] Featuring Tunable Dual Luminescence Properties

Abstract

Five Tb3+/Eu3+ mixed nonanuclear clusters with the general formula [Eu9–xTbx(acac)16(µ3‐OH)8(µ4‐O)(µ4‐OH)] ([Eu9–xTbx], x = 0.9–8.1, acac = acetylacetonate) were synthesized. Characterization by powder X‐ray diffraction (PXRD), energy‐dispersive X‐ray spectroscopy (EDS) and inductively coupled plasma optical emission spectroscopy (ICP‐OES) highlight a near‐perfect match between the amounts of Tb3+ and Eu3+ ions input in the reaction mixture and the amounts in the clusters. The luminescence properties of these [Eu9–xTbx] clusters were investigated thoroughly in the solid state, and a strong energy transfer from the Tb3+ to Eu3+ emitters was evidenced. Thus, these nano‐nonanuclear 4f clusters, which can be viewed as square pyramids that share one top, exhibit dual luminescence that can be adjusted by controlling the ratio of the lanthanide ions within the crystal architecture.

Upconversion in molecular hetero-nonanuclear lanthanide complexes in solution

“…Among known lanthanide (Ln) complexes, 10 a family based on β-diketonate ligands attracted our attention as a result of their straightforward synthesis, 11 versatility in nuclearity 12 and composition, 13 and short inter-Ln distances. 14 The simple case of acetylacetonate ligands forming nonanuclear complexes 12 particularly piqued our interest with the close proximity of up to nine Ln atoms in a very small volume and intermetallic distances shorter than 5 Å. Noteworthy, a controlled doping of such complexes might allow the formation of entities containing up to eight sensitizing ions for one emitting UC center, a situation considered to be optimum for maximizing energy transfer UC.…”

Luminescence‐Driven Electronic Structure Determination in a Textbook Dimeric DyIII‐Based Single‐Molecule Magnet

“…to isolate à la carte polynuclear complexes. [47][48][49][50] Herein, we report at extbook dysprosium dinuclear complex based on the acetylacetonate ligand (the simplest diketonate).The goal of this work is to use seminalc rystal field approacht om arry magnetism and luminescenceinthe frame of an energetic picture.…”

“…Although these pincers can present several coordination modes, it is possible by controlling the synthesis parameters (pH, temperature, time, etc.) to isolate à la carte polynuclear complexes . Herein, we report a textbook dysprosium dinuclear complex based on the acetylacetonate ligand (the simplest diketonate).…”

Upconversion in Molecular Hetero-Nonanuclear Lanthanide Clusters in Solution

“…Among known lanthanide (Ln) clusters, 10 a family based on βdiketonate ligands attracted our attention as a result of their straightforward synthesis, 11 versatility in nuclearity 12 and composition, 13 and small inter-Ln distances. 14 The simple case of acetylacetonate ligands forming nonanuclear clusters 12 particularly retained our interest with the close proximity of up to nine Ln atoms in a very small volume and intermetallic distances shorter than 5 Å. Noteworthy, a controlled doping of such clusters might allow the formation of clusters containing up to eight sensitizing ions for one emitting UC center, a situation considered to be optimum for maximizing energy transfer UC.…”