Accelerated Syntheses of Porous Isostructural Lanthanide–Benzenetricarboxylates (Ln–BTC) Under Ultrasound at Room Temperature

Abstract

Porous isostructural [Ln(BTC)(H2O)·4.3H2O], or Ln–BTC (Ln: Ce, Tb, and Y; BTC stands for 1,3,5‐benzenetricarboxylate), with a tetragonal structure has been synthesized by ultrasonic irradiation at room temperature. Under ultrasound, the syntheses were quickly accelerated to obtain the fully crystallized phase in only minutes. The particle size can be considerably decreased by this method. On the basis of XRD, field‐emission scanning electron microscopy (FE‐SEM), and surface area analyses, it can be understood that the Ln–BTCs are homogeneous in phase, isostructural, and microporous. The synthesis rates are rCe–BTC > rTb–BTC > rY–BTC for both in the nucleation and crystal‐growth stages, thereby illustrating the importance of the lability of the metal ions in the synthesis of the metal‐organic framework (MOF) materials. The Tb–BTC shows luminescence properties, a characteristic property of Tb3+ (green‐light emission), in the range of 470–630 nm at room temperature. It is believed that these lanthanide MOFs with micropores and/or luminescent properties should be proven to be multifunctional materials on further investigations.

Eu3+-Mediated Polymerization of Benzenetetracarboxylic Acid Studied by Spectroscopy, Temperature-Dependent Calorimetry, and Density Functional Theory

“…The proposed structural model provides a consistent explanation for the stoichiometry and heat uptake measured by ITC as well as for the spectral properties of the lanthanide coordinated in the monomeric or polymeric state. The data are thus consistent with formation of metal-linked polymers as described for benzenemulticarboxylates 12,42À45 and several polymeric lanthanide BTC complexes, 13,14,46,47 where also mainly a 1:1 metal-toligand stoichiometry is observed.…”

Rare earth based nanostructured materials: synthesis, functionalization, properties and bioimaging and biosensing applications

“…Bubbles are formed in solution, and after their collapse, local points of very high temperature and pressure can be produced [136]. Sonochemical synthesis can be carried out at room conditions, as it was reported for a series of RE-benzenetricarboxylates MOFs (RE = Ce, Tb, Y) [137]. Spray-based methods have also been reported in the literature.…”

Group 3 Elements and Lanthanide Metals

“…They include 17 elements: Sc, Y, and La (21, 39, and 57) as well as Ce-Lu (58)(59)(60)(61)(62)(63)(64)(65)(66)(67)(68)(69)(70)(71). The only exception not addressed in this chapter is promethium (61) that plays no role in MOF chemistry due to the radioactivity of its isotopes.…”