Catalytic Performance and Electrophoretic Behavior of an Yttrium–Organic Framework Based on a Tricarboxylic Asymmetric Alkyne

Abstract

A new Y-based metal−organic framework (MOF) GR-MOF-6 with a chemical formula of {[YL(DMF) 2 ]•(DMF)} n {H 3 L = 5-[(4-carboxyphenyl)ethynyl] isophthalic acid; DMF = N,N-dimethylfor-mamide} has been prepared by a solvothermal route. Structural characterization reveals that this novel material is a three-dimensional MOF in which the coordination of the tritopic ligand to Y(III) metal ions leads to an intercrossing channel system extending over three dimensions. This material has proven to be a very efficient catalyst in the cyanosilylation of carbonyls, ranking second in catalytic activity among the reported rare earth metal-based MOFs described so far but with the lowest required catalyst loading. In addition, its electrophoretic behavior has been studied in depth, providing a zero-charge point between pH 4 and 5, a peak electrophoretic mobility of −1.553 μm cm V −1 s −1 , and a ζ potential of −19.8 mV at pH 10.

A Mixed Heterobimetallic Y/Eu-MOF for the Cyanosilylation and Hydroboration of Carbonyls

“…The obtained values for cyanosilylation reaction were 100% of AE, 1.127 for MI, 95.7% for RME, and 96.8% for CE. These results are comparable to those described previously for related lanthanide-based MOFs [15,16,19,20]. In the case of the hydroboration reaction, these values decreased considerably, down to 49.1%, 2.406, 46.8%, and 52.1% for AE, MI, RME, and CE, respectively, due to the final hydrolysis and consequent loss of atoms in the final product (Table S9).…”

“…Nonetheless, within this frame of reference, the number of reported Ln-MOF acting as a heterogeneous catalyst in the cyanosilylation reaction results were relatively scarce 2 of 10 (Table S10 summarizes the reported examples exhibiting activity, so far) [5,[9][10][11][12][13][14][15][16][17][18][19][20][21][22][23][24]. Moreover, to the best of our knowledge, lanthanide-based heterobimetallic MOFs have never been applied.…”

“…The synthesis of alcohols through this route has been explored via MOF systems based on Ti, Fe, Co, and Mg [25][26][27][28][29][30]; however, there are no precedents with these supramolecular entities built on lanthanides precursors. Therefore, in this work, the first example of yttrium and europiumbased mixed MOF, with the formula {[Y 3.5 Eu 1.5 L 6 (OH) 3 (H 2 O) 3 ]•12DMF} n , is presented, taking the strong background of our group in the examination of these supramolecular systems in catalysis [15,16].…”

Nonredox CO2 Fixation in Solvent-Free Conditions Using a Lewis Acid Metal–Organic Framework Constructed from a Sustainably Sourced Ligand

“…In this work, we have successfully synthesized two new FDC-based MOFs: UOW-1 and UOW-2 (UOW indicates “University of Warwick”) having chemical formulas of {Y 3 (HFDC)­(FDC) 4 (H 2 O) 6 }·3H 2 O and {Y 2 (FDC) 2 (H 2 O) 10 }­FDC·6H 2 O, respectively. The choice of yttrium (Y 3+ ) as the metal center is primarily due to its characteristic Lewis acidic nature (arising from the d -orbital vacancy), which can facilitate catalytic reactions . Consequently, the MOFs have been applied as catalysts for solvent-free CO 2 epoxidation reactions to yield cyclic carbonates with high conversion rates and selectivity.…”

“…The choice of yttrium (Y 3+ ) as the metal center is primarily due to its characteristic Lewis acidic nature (arising from the d -orbital vacancy), which can facilitate catalytic reactions. 26 Consequently, the MOFs have been applied as catalysts for solvent-free CO 2 epoxidation reactions to yield cyclic carbonates with high conversion rates and selectivity. UOW-1 emerged as the best catalyst for CO 2 epoxidation with high turnovers compared to UOW-2 and a Y-centered MOF based on common BDC linkers, which was used for comparison.…”