Lanthanide metal organic frameworks based on dicarboxyl-functionalized arylhydrazone of barbituric acid: syntheses, structures, luminescence and catalytic cyanosilylation of aldehydes

Abstract

Five isostructural lanthanide MOFs, [Ln(1κOO',2κO'',3κO''',4κO''''-μ-L)(NO)(DMF)]·n(DMF) {Ln = La (1), Ce (2), Nd (3), Sm (4) and Dy (5); L = 5-[2-{2,4,6-trioxotetrahydropyrimidin-5(2H)-ylidene}hydrazinyl]isophthalate; DMF = N,N'-dimethyl formamide}, based on dicarboxyl-functionalized arylhydrazone of barbituric acid were synthesized under solvothermal conditions. They were characterized by elemental analysis, FT-IR spectroscopy, thermogravimetric and X-ray diffraction analyses. Crystal structure analysis revealed that these frameworks possess a similar type of two dimensional (2D) structure with a dinuclear {Ln(COO)} unit acting as a secondary building block. Topological analysis shows that these frameworks display a 3,6-connected kgd; Shubnikov plane (3.6.3.6)/dual net. They exhibit excellent heterogeneous catalytic activities (compound 2 is the most active one) towards the cyanosilylation of aldehydes under solvent-free conditions. These catalysts can be recycled at least up to five cycles without a loss of activity. Compounds 1-5 exhibit luminescence properties in the solid state at room temperature.

Noncovalent Interactions at Lanthanide Complexes

“…As expected, all structures ( 16 – 20 ) are isostructural, but the N⋅⋅⋅O distance in the RAHB system slightly increases in the following order: La ( 16 )=Ce ( 17 )<Nd ( 18 )<Sm ( 19 )<Dy ( 20 ) (Scheme 6). Furthermore, there is no trend between the N⋅⋅⋅O distance and yield (%) of 2‐phenyl‐2‐((trimethylsilyl)oxy)acetonitrile in 16 – 20 catalysed cyanosilylation of benzaldehyde with trimethylsilyl cyanide: 89 ( 19 )<90 ( 20 )<91 ( 18 )<93 ( 16 )<94 % ( 17 ) [51] …”

Crystal structure and Hirshfeld analysis of di-tert-butyl 2,2′-[(ethylazanediyl)bis(methylene)]bis(1H-pyrrole-1-carboxylate)

“…However, taking into account the importance of the noncovalent bond-donor/acceptor properties of the nitrogen atom in N-heterocycles for synthesis, catalysis and the design of new materials (Asadov et al, 2016;Gurbanov et al, 2017Gurbanov et al, , 2018aKarmakar et al, 2017;Maharramov et al, 2018;Mahmoudi et al, 2017Mahmoudi et al, , 2019Mahmudov et al, 2010Mahmudov et al, , 2013Mahmudov et al, , 2017aMahmudov et al, ,b, 2019Mahmudov et al, , 2020Shixaliyev et al, 2014), we describe in this work the structural features of compound 4.…”

Highly Efficient Bifunctional Amide Functionalized Zn and Cd Metal Organic Frameworks for One-Pot Cascade Deacetalization–Knoevenagel Reactions

“…Besides that, these materials can be directly implanted with catalytically active centers (acidic and basic groups) either in the ligands or metal centers, which can make them a unique material for multifunctional heterogeneous catalysis (Wen et al, 2018). In this context, our group recently developed several amide functionalized MOFs where the amide group serves as a Lewis basic center and the metal as Lewis acid, which is quite effective for catalyzing various reactions such as oxidation of alkenes and alcohols, transesterification, Knoevenagel condensation, cyanosilylation, and the Henry reaction (Karmakar et al, 2017; Karmakar and Pombeiro, 2019; Liu et al, 2019).…”