Gram-Scale Synthesis of Cu(II)@COF via Solid-State Coordination Approach for Catalysis of Alkyne-Dihalomethane-Amine Coupling

Abstract

A novel covalent organic framework material COF-DM, which contains chelating coordination environments, was synthesized at the gram level under mild conditions. In addition, its Cu­(II)-loaded complex of Cu­(II)@COF-DM was prepared by impregnating COF-DM in an acetonitrile solution of CuCl2 via a solid-state coordination approach. The obtained Cu­(II)-loaded Cu­(II)@COF-DM can be used as a highly active heterogeneous catalyst to catalyze the alkyne-dihalomethane-amine coupling reactions.

Bimetallic docked covalent organic frameworks with high catalytic performance towards coupling/oxidation cascade reactions

“…3d). 50,51 The shift downfield of both Cu 2p and Pd 3d signals can be attributed to the donor–acceptor interaction occurring through the coordination bonds between metal ions and the COF. 52 Considering that the catalyst was dried before, it is likely that a little amount of Cu with different valence state, like Cu( i ) and Cu(0) was produced that participated in the catalysis.…”

Synthesis of Chiral Covalent Organic Frameworks via Asymmetric Organocatalysis for Heterogeneous Asymmetric Catalysis

“…The Cu II loading, however, did not change the CCOF structure and chirality but reduced its surface area and pore size (Supporting Information, Figure S7). The Cu 2p 3/2 and Cu 2p 1/2 peaks at 934.6 and 954.5 eV in its X‐ray photoelectron spectroscopy (XPS) spectrum indicated that the loaded Cu valence was bivalent (Supporting Information, Figure S7) [21b] . SEM‐EDX mapping showed that the C, O, N, and Cu elements were homogeneously distributed in Cu II @( Λ )‐TpPa‐1 (Supporting Information, Figure S7).…”

Porous organic–inorganic hybrid materials for catalysis, energy and environmental applications

“…Recently, Kan et al synthesized a novel covalent organic framework, COF-DM, on the gram-level scale via the aldimine condensation reaction between 1,4-dibenzoylhydrazinyl-2-methylbenzene (DBHMB) and 2,4,6-trihydroxy-1,3,5-benzenetricarbaldehyde (MOP) under mild conditions. 131 This yellow crystalline solid COF-DM generated numerous chelating coordination environments inside the solid matrix, which stabilized and bound the Cu 2+ ions when treated with a CuCl 2 acetonitrile solution, yielding a yellow-brown crystalline Cu(II)@COF-DM. This material showed high catalytic activity for the alkyne-dihalomethane-amine (AHA) coupling reaction with 1,8-diazabicyclo[5.4.0]undec-7ene (DBU) and CH 3 CN as the base and solvent, respectively, producing 99% yield in the model reaction.…”