Heterometallic Europium(III)-Lutetium(III) Terephthalates as Bright Luminescent Antenna MOFs

Abstract

A new series of luminescent heterometallic europium(III)-lutetium(III) terephthalate metal-organic frameworks, namely (Eu_xLu_1-x)₂bdc₃·nH₂O, was synthesized using a direct reaction in a water solution. At the Eu³⁺ concentration of 1-40 at %, the MOFs were formed as a binary mixture of the (Eu_xLu_1-x)₂bdc₃ and (Eu_xLu_1-x)₂bdc₃·4H₂O crystalline phases, where the Ln₂bdc₃·4H₂O crystalline phase was enriched by europium(III) ions. At an Eu³⁺ concentration of more than 40 at %, only one crystalline phase was formed: (Eu_xLu_1-x)₂bdc₃·4H₂O. All MOFs containing Eu³⁺ exhibited sensitization of bright Eu³⁺-centered luminescence upon the 280 nm excitation into a ¹ππ* excited state of the terephthalate ion. The fine structure of the emission spectra of Eu^{3+ 5}D₀-⁷F_J (J = 0-4) significantly depended on the Eu³⁺ concentration. The luminescence quantum yield of Eu³⁺ was significantly larger for Eu-Lu terephthalates containing a low concentration of Eu³⁺ due to the absence of Eu-Eu energy migration and the presence of the Ln₂bdc₃ crystalline phase with a significantly smaller nonradiative decay rate compared to the Ln₂bdc₃·4H₂O.

Keywords: europium; luminescence; lutetium; metal–organic framework; phase transition; rare earth.