A Metal–Organic Framework to CuO Nanospheres of Uniform Morphology for the Synthesis of α-Aminonitriles under Solvent-Free Condition along with Crystal Structure of the Framework

Abstract

Herein, we have reported the synthesis, crystal structure, thermogravimetric property, and photoluminescence activity of a new Cu-based metal organic framework (MOF): {[Cu2(2,5-pdc)2­(ald-4)­(H2O)2]­·3H2O,MeOH} n (where 2,5-pdc = 2,5-pyridine-dicarboxylate, ald-4 = aldrithiol-4) along with catalytic activity of CuO nanoparticles (Cu-NPs) derived from the MOF for green synthesis of organic molecules having biological relevance. The regular arrangement of metal centers and the presence of oxygen and carbon in metal–organic frameworks (MOFs) enable us to utilize them as template/precursor for the synthesis of monodispersed metal-oxide and metal-carbide nanoparticles having a high surface area with well-defined and uniform morphology. The MOF derived oxide nanoparticles generally exhibit improved catalytic activities and product selectivity and significantly reduce the chemical waste production. The structural analysis has revealed that in the complex under investigation the 2,5-pdc bridges the Cu­(II) centers to form both left-handed and right-handed infinite one-dimensional helical chains, and the complex is a three-dimensional achiral framework composed of neighboring two-dimensional sheets of opposite chirality. The thermogravimetric study suggests that the framework is stable up to 500 °C. Single phase, highly crystalline, nearly monodispersed, and spherical CuO-NPs having an average particle size of ∼27.9 nm has been synthesized by heating the framework at 650 °C for 4 h. The CuO-NPs are characterized by using powder X-ray diffraction, high resolution transmission electron microscopy, selected area electron diffraction, energy dispersive X-ray spectroscopy, and dynamic light scattering technique. Further, the crystal structure of the CuO-NPs has also been illustrated by Rietveld refinement of powder pattern. Finally, the as-synthesized CuO-NPs were employed in the one-pot three component Strecker synthesis of α-aminonitriles via the condensation of benzaldehyde, aniline, and trimethylsilyl cyanide under solvent-free condition. This work will be helpful in utilizing the MOF derived oxide nanoparticles for development of sustainable chemical processes.

Synthesis of UiO-66-Pyca-CuO by a Simple and Novel Method: MOF-based Metal Thin Film as Heterogeneous Catalysts for the Synthesis of α-Aminonitriles

“…The XRD pattern showed that this compound is crystalline, and the UiO-66-Pyca-CuO pattern closely resembled that of UiO-66-NH 2 , although differences in peak intensities were observed. This is associated with the unique morphology of the flower-like CuO nanosheets (Figure c). , …”

Crystal structure of 4,4′-(disulfanediyl)dipyridinium chloride triiodide

“…Although 4,4 0 -dipyridyldisulfide (L 0 ) has been widely reported as a donor towards a variety of metal ions (Sarkar et al, 2016;Zheng et al, 2022Zheng et al, , 2023Singha et al, 2018), its reactivity towards halogens or interhalogens has been only marginally explored (Wzgarda-Raj et al, 2021;Coe et al, 1997). An example is provided by 4,4 0 -(disulfanediyl)dipyridinium pentaiodide triiodide (CSD code OXAFIF; Wzgarda-Raj et al, 2021) where the cation H 2 L 02+ is counterbalanced by a polyiodide built up of interacting I 3 À and I 5 À ions.…”

Palladium and Copper: Advantageous Nanocatalysts for Multi-Step Transformations

“…Reusability of the catalyst was demonstrated since no loss of activity was detected after 10 runs. Saha et al prepared CuONPs by thermal decomposition of a previously synthesized two-dimension copper organic framework (2D-(Cu)COF) [170]. 2D coordination polymer was characterized by single-crystal XRD prior decomposition.…”