Brightly Luminescent (Tb_xLu_1-x)₂bdc₃·nH₂O MOFs: Effect of Synthesis Conditions on Structure and Luminescent...

Luminescent, heterometallic terbium(III)-lutetium(III) terephthalate metal-organic frameworks (MOFs) were synthesized via direct reaction between aqueous solutions of disodium terephthalate and nitrates of corresponding lanthanides by using two methods: synthesis from diluted and concentrated solutions. For (Tb_xLu_1-x)₂bdc₃·nH₂O MOFs (bdc = 1,4-benzenedicarboxylate) containing more than 30 at. % of Tb³⁺, only one crystalline phase was formed: Ln₂bdc₃·4H₂O. At lower Tb³⁺ concentrations, MOFs crystallized as the mixture of Ln₂bdc₃·4H₂O and Ln₂bdc₃·10H₂O (diluted solutions) or Ln₂bdc₃ (concentrated solutions). All synthesized samples that contained Tb³⁺ ions demonstrated bright green luminescence upon excitation into the ¹ππ* excited state of terephthalate ions. The photoluminescence quantum yields (PLQY) of the compounds corresponding to the Ln₂bdc₃ crystalline phase were significantly larger than for Ln₂bdc₃·4H₂O and Ln₂bdc₃·10H₂O phases due to absence of quenching from water molecules possessing high-energy O-H vibrational modes. One of the synthesized materials, namely, (Tb_0.1Lu_0.9)₂bdc₃·1.4H₂O, had one of the highest PLQY among Tb-based MOFs, 95%.