Construction of the Copper‐Functionalized Covalent Organic Framework Used as a Heterogeneous Catalyst for Click Reaction

Abstract

Functional modification of the covalent organic frameworks (COFs) has become an efficient strategy to expand its applications in various fields. In this investigation, an imine linked T−D COF has been synthesized via solvothermal method using 2,4,6‐tris(4‐aminophenyl)pyridine (TAPP) and 2,6‐dihydroxynaphthalene‐1,5‐dicarbaldehyde (DHNDA) as building blocks. While synthesizing T‐D COF, hydroxyl groups are strategically introduced to the adjacent sites of −C=N− bonds in the framework. Such a special structure enables a strong coordination between the loaded copper metal ion and the hydroxyl groups together with imine bounds in the COF layered structure. The obtained copper‐containing COF, (Cu@T−D COF) hybrid material was used as an efficient heterogeneous catalyst for the alkyne‐azide click chemistry reactions and showed excellent catalytic activity in methanol/water medium. Furthermore, this Cu@T−D COF is stable and easily recycled and reused without loss of its catalytic activity.

Scalable Fabrication of Crystalline COF Membranes from Amorphous Polymeric Membranes

“…2.82° for TAPT‐DHNDA assigned to the (100) reflection plane can be observed in the PXRD pattern, which substantiates its ordered crystalline structures. Moreover, the experimental PXRD pattern of TAPT‐DHNDA is in good consistence with the simulated patterns calculated from AA stacking model (Figure 4 c, S14 and Table S2) and the previous report [32] . Crystalline TAPT‐DHNDA membrane demonstrates the morphology of randomly well‐intergrown grains (Figure 4 e).…”

Metalated covalent organic frameworks: from synthetic strategies to diverse applications

“…In 2020, Gao and co-workers reported the Cu@T-D COF by metalating the ( E )-1-((phenylimino)methyl)naphthalen-2-ol moiety in the T-D COF. 293 Since the T-D COF contains pyridyl donors, the definite location of Cu( ii ) deserves further study.…”

“…In 2020, Gao et al demonstrated that the click reaction of terminal alkynes with azides can be achieved by a Cu( ii )-functionalized COF with sodium ascorbate as the reducing agent. 293 For the reaction of phenylacetylene with benzyl azide at 60 °C, the yields in methanol, ethanol, acetonitrile, and water are all above 80%, and the reaction proceeds almost quantitatively in a mixed solvent system of methanol and water. However, the reducing agent used in this reaction cannot be recovered, which increases the cost of the reaction.…”

Scalable Fabrication of Crystalline COF Membranes from Amorphous Polymeric Membranes

“…2.828 8 for TAPT-DHNDAassigned to the (100) reflection plane can be observed in the PXRD pattern, which substantiates its ordered crystalline structures.M oreover, the experimental PXRD pattern of TAPT-DHNDAisin good consistence with the simulated patterns calculated from AA stacking model (Figure 4c,S 14 and Table S2) and the previous report. [32] Crystalline TAPT-DHNDAm embrane demonstrates the morphology of randomly well-intergrown grains (Figure 4e). TGA curve (Figure S15) reveals that TAPT-DHNDAm embrane is stable up to ca.…”