Visible and near-infrared emission from lanthanoid β-triketonate assemblies incorporating cesium cations

Laura Abad Galán, Brodie L. Reid, Stefano Stagni, Alexandre N. Sobolev, Brian W. Skelton, Massimo Cocchi, Joanna M. Malicka, Eli Zysman-Colman, Evan G. Moore, Mark I. Ogden, Massimiliano Massi

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Abstract

The reaction of the β-triketonate ligands tris(4-methylbenzoyl)methanide and tribenzoylmethanide with the trivalent lanthanoid Eu3+, Er3+, and Yb3+ in the presence of Cs+ afforded polymeric structures where the repeating units are represented by bimetallic tetranuclear assemblies of formulation {[Ln(Cs)(β-triketonate)4]2}n. The only exception is the structure formed by reaction of tris(4-methylbenzoyl)methanide, Yb3+, and Cs+, which yielded a polymeric assembly where the repeating units are mononuclear Yb3+ complexes bridged by Cs+ cations. Photophysical measurements on the obtained materials confirmed efficient sensitization from the ligand excited states to the 4ƒ* excited stated of the three lanthanoids. According to transient absorption data, Er3+ and Yb3+ are sensitized via energy transfer from the triplet state of the β-triketonate ligands. On the other hand, energy transfer to Eu3+ seems to occur via an alternative pathway, possibly directly via the singlet state or through ligand-to-metal charge transfer states. The emission measurements confirm efficient sensitization for all three lanthanoids and bright near-infrared emission for Er3+ and Yb3+, a characteristic that seems to be linked to the specific chemical structure of the β-triketonate ligands.
Original languageEnglish
Pages (from-to)8975-8985
Number of pages11
JournalInorganic Chemistry
Volume56
Issue number15
Early online date11 Jul 2017
DOIs
Publication statusPublished - 7 Aug 2017

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