A versatile Cu^II/Cu^Imetal–organic framework for selective sorption and heterogeneous catalysis

Abstract

A three-dimensional (3-D) multi-functional mixed valence Cu II /Cu I -MOF, {[Cu(CuI)2(2-pyzc)2H2O]2·H2O}n, (Hpyzc=pyrazine-2dicarboxylic acid), has been solvothermally synthesized and successfully characterized by FT-IR spectroscopy, elemental analysis, powder X-ray diffraction, thermal gravimetric analysis (TGA) and single-crystal X-ray diffraction. The structure posesses a 3-D open framework containing 1-D channels and shows tcj topological network with the Schläfli Symbol of (4 3 .6 12 ) (4 3 )2. This MOF exhibits selective adsorption of CO2/H2 over CH4/N2 and excellent catalytic activity in the oxidation of benzylic compounds and three-component coupling reactions of aromatic alkynes, tosylazide and diisopropylamine as a cooperative catalyst. The catalyst could be reused several times without significant degradation in catalytic activity.

Bifunctional 2D Cd(II)-Based Metal–Organic Framework as Efficient Heterogeneous Catalyst for the Formation of C–C Bond

“…We have been studying the design of functionalized MOFs and their application for heterogeneous catalysis. − As reported in our previous work, we obtained a polyhedral metal–organic framework, [Eu 2 (PDC) 3 ] (H 2 PDC = pyridine-3,5-dicarboxylic acid), which could effectively accelerate the cyanosilylation reaction . By utilizing a versatile Cu II /Cu I metal–organic framework as catalyst, three-component coupling reactions of diisopropylamine, tosylazide, and aromatic alkynes can be promoted as well as the oxidation of benzylic compounds . As part of our continuous work, herein, we reported the synthesis and characterization of a 2D (3,6)-connected framework with kgd topology, namely, [Cd­(PBA)­(DMF)]·DMF (H 2 PBA = 5-(4-pyridin-3-yl-benzoylamino)-isophthalic acid).…”

“…25 By utilizing a versatile Cu II /Cu I metal−organic framework as catalyst, three-component coupling reactions of diisopropylamine, tosylazide, and aromatic alkynes can be promoted as well as the oxidation of benzylic compounds. 26 As part of our continuous work, herein, we reported the synthesis and characterization of a 2D (3,6)connected framework with kgd topology, namely, [Cd(PBA)-(DMF)]•DMF (H 2 PBA = 5-(4-pyridin-3-yl-benzoylamino)isophthalic acid). Moreover, the catalytic properties were also studied.…”

Air‐Induced One‐Pot Synthesis of N‐Sulfonylformamidines from Sulfonyl Chlorides, NaN3, and Tertiary/Secondary Amines

“…However, Hinsberg reaction generally suffers from several drawbacks, such as narrow reaction scopes, unsatisfactory yields and unavailable starting materials (Scheme a). In recent years, Cu‐catalyzed three‐component coupling reactions of sulfonyl azides, alkynes, and secondary amines have been well explored and applied for the synthesis of N ‐sulfonylamidines . In this kind of reactions, some by‐products are easily formed, such as alkyne–alkyne coupling products and triazole, which significantly decrease the yield of N ‐sulfonylamidines.…”

Mixed-valence copper(i,ii) complexes with 4-(1H-pyrazol-1-yl)-6-R-pyrimidines: from ionic structures to coordination polymers

“…[32][33][34][35][36][37][38][39][40] Copper(I,II) complexes can show electrical conductivity, [41][42][43] magnetic activity, [44][45][46][47] dielectric properties, 48 redox activity 49 and luminescence. 50 Catalytic activity 51 and absorbing properties 52,53 of copper(I,II) mixed valence compounds are being studied. Copper(I,II) complexes can be regarded as models for coppercontaining metallo-enzymes.…”