The reaction of hydrated lanthanoid chlorides with tribenzoylmethane and an alkali metal hydroxide consistently resulted in the crystallization of neutral tetranuclear assemblies with the general formula [Ln(Ae·HOEt)(L)4]2 (Ln= Eu3+, Er3+, Yb3+; Ae=Na+, K+, Rb+). Analysis of the Crystal structures of these species revealed a coordination geometry that varied from a slightly distorted square antiprism to a slightly distorted triangular dodecahedron, with the specific geometrical shape being dependent on the degree of lattice solvation and identity of the alkali metal. The near-infrared (NIR)-emitting assemblies of Yb3+ and Er3+ showed remarkably efficient emission, characterized by significantly longer excited-state lifetimes (tobs …37–47 ms for Yb3+ and tobs …4–6 ms for Er3+) when compared with the broader family of lanthanoid b-diketonate species, even in the case of perfluorination of the ligands. The Eu3+ assemblies show bright red emission and a luminescence performance (tobs …0.5 ms, FL Ln …35–37 %, hsens …68–70%) more akin to the bdiketonate species. The results highlight that the b-triketonate ligand offers a tunable and facile system for the preparation of efficient NIR emitters without the need for more complicated perfluorination or deuteration synthetic strategies.

Lanthanoid/Alkali Metal β-Triketonate Assemblies: A Robust Platform for Efficient NIR Emitters / Reid, Brodie L.; Stagni, Stefano; Malicka, Joanna M.; Cocchi, Massimo; Sobolev, Alexandre N.; Skelton, [e] Brian W.; Moore, [e] Evan G.; Hanan, [f] Garry S.; Ogden, Mark I.; Massi, Massimiliano. - In: CHEMISTRY-A EUROPEAN JOURNAL. - ISSN 0947-6539. - STAMPA. - 21:(2015), pp. 18354-18363. [10.1002/chem.201502536]

Lanthanoid/Alkali Metal β-Triketonate Assemblies: A Robust Platform for Efficient NIR Emitters

STAGNI, STEFANO;MASSI, MASSIMILIANO
2015

Abstract

The reaction of hydrated lanthanoid chlorides with tribenzoylmethane and an alkali metal hydroxide consistently resulted in the crystallization of neutral tetranuclear assemblies with the general formula [Ln(Ae·HOEt)(L)4]2 (Ln= Eu3+, Er3+, Yb3+; Ae=Na+, K+, Rb+). Analysis of the Crystal structures of these species revealed a coordination geometry that varied from a slightly distorted square antiprism to a slightly distorted triangular dodecahedron, with the specific geometrical shape being dependent on the degree of lattice solvation and identity of the alkali metal. The near-infrared (NIR)-emitting assemblies of Yb3+ and Er3+ showed remarkably efficient emission, characterized by significantly longer excited-state lifetimes (tobs …37–47 ms for Yb3+ and tobs …4–6 ms for Er3+) when compared with the broader family of lanthanoid b-diketonate species, even in the case of perfluorination of the ligands. The Eu3+ assemblies show bright red emission and a luminescence performance (tobs …0.5 ms, FL Ln …35–37 %, hsens …68–70%) more akin to the bdiketonate species. The results highlight that the b-triketonate ligand offers a tunable and facile system for the preparation of efficient NIR emitters without the need for more complicated perfluorination or deuteration synthetic strategies.
2015
Lanthanoid/Alkali Metal β-Triketonate Assemblies: A Robust Platform for Efficient NIR Emitters / Reid, Brodie L.; Stagni, Stefano; Malicka, Joanna M.; Cocchi, Massimo; Sobolev, Alexandre N.; Skelton, [e] Brian W.; Moore, [e] Evan G.; Hanan, [f] Garry S.; Ogden, Mark I.; Massi, Massimiliano. - In: CHEMISTRY-A EUROPEAN JOURNAL. - ISSN 0947-6539. - STAMPA. - 21:(2015), pp. 18354-18363. [10.1002/chem.201502536]
Reid, Brodie L.; Stagni, Stefano; Malicka, Joanna M.; Cocchi, Massimo; Sobolev, Alexandre N.; Skelton, [e] Brian W.; Moore, [e] Evan G.; Hanan, [f] Garry S.; Ogden, Mark I.; Massi, Massimiliano
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11585/545362
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