Characterization and Luminescence Properties of Lanthanide-Based Polynuclear Complexes Nanoaggregates

Abstract

For the first time, hexanuclear complexes with general chemical formula [Ln6O(OH)8(NO3)6(H2O)n](2+) with n = 12 for Ln = Sm-Lu and Y and n = 14 for Ln = Pr and Nd were stabilized as nanoaggregates in ethylene glycol (EG). These unprecedented nanoaggregates were structurally characterized by (89)Y and (1)H NMR spectroscopy, UV-vis absorption and luminescence spectroscopies, electrospray ionization mass spectrometry, diffusion ordered spectroscopy, transmission electron microscopy, and dynamic light scattering. These nanoaggregates present a 200 nm mean solvodynamic diameter. In these nanoaggregates, hexanuclear complexes are isolated and solvated by EG molecules. The replacement of ethylene glycol by 2-hydroxybenzyl alcohol provides new nanoaggregates that present an antenna effect toward lanthanide ions. This results in a significant enhancement of the luminescence properties of the aggregates and demonstrates the suitability of the strategy for obtaining highly tunable luminescent solutions.

Strongly Coupled Cyclometalated Ruthenium–Triarylamine Hybrids: Tuning Electrochemical Properties, Intervalence Charge Transfer, and Spin Distribution by Substituent Effects

“…These experiments suggested that the coordination polymers were solvated by glycerol molecules (GLY). This phenomenon has previously been observed with ethylene glycol for polyoxometalates,32 gold nanoparticles,33 and lanthanide complexes,8 but, to the best of our knowledge, this is the first time that it has been observed for lanthanide‐based coordination polymers. The solvated nanoparticles are hereinafter denoted by [Tb 2 (bdc) 3 ⋅ 4 H 2 O] ∞ @GLY and [Eu 2 (bdc) 3 ⋅ 4 H 2 O] ∞ @GLY.…”

Nanometrization of Lanthanide‐Based Coordination Polymers

“…These experiments suggestedt hat the coordination polymersweresolvated by glycerol molecules (GLY). This phenomenon has previously been observed with ethylene glycol for polyoxometalates, [32] gold nanoparticles, [33] and lanthanide complexes, [8] but, to the best of our knowledge, this is the first time that it has been observed for lanthanide-based coordination polymers. The solvated nanoparticles are hereinafter denotedb y[ Tb 2 (bdc) 3 ·4H 2 O] 1 @GLYa nd [Eu 2 (bdc) 3 ·4H 2 O] 1 @GLY.…”

“…Lanthanide-based coordinationc ompounds have attracted great attention because of their uniquel uminescenceproperties. [2][3][4][5] The synthesis of tailoredhetero-lanthanide complexes has led to fascinating materials, [6][7][8] but their cost constitutes as eriousd rawback as far as surfacel ighting or the fight againstc ounterfeiting are concerned.M oreover,i n heteronuclear complexes, the number of lanthanide ions is limited and hence also the tuning of their luminescence properties. On the contrary,h eteronuclear lanthanide-based coordination polymers are characterizedb yalarge number of metallic sites even at the nanometrics cale.…”

Functionalised phosphonate ester supported lanthanide (Ln = La, Nd, Dy, Er) complexes

“…assigned to electronic orbital interactions between f-orbitals of the rare-earth metal centres and, in the case of this cluster, the oxygen-centred orbitals of an adjacent oxo-ligand. 42 Such an electrostatic ligand effect could also be observed for the electronic structure of a variety of mono-lanthanide species by Furet et al 38 Hence, the less pronounced splitting in the monomeric complexes 18, 26 and 30 can most likely be assigned as well to such a type of interaction.…”