Abstract
The coordination polymer [Cu2(TDPH)4(QNX)].DMF, (QNX = Quinoxaline; TDPH = 3,3-thiodipropionic acid), has been prepared by reaction of copper acetate, TDPH, and quinoxaline. The compound was characterized by elemental analysis, FTIR spectroscopy, and single-crystal X-ray diffraction. The crystal is monoclinic with a P21/n space group and dimensions of a = 12.889(3) Å, b = 14.983(4) Å, c = 14.091(3) Å, α = 90°, β = 90.200(11)°, γ = 90°, V = 2721.18 (2) Å3, Z = 4. The ligands are hexagonally coordinated to the Cu(II) centre in the form of Cu2O4N with one nitrogen atom from the quinoxaline ligand, and four oxygen atoms from four TDPH molecules in a monodentate fashion. The Cu–Cu bond length was 2.642(1) and 2.629(1) Å for the Cu1–Cu1 and Cu2–Cu2 bonds. The QNX ligand bridged the two copper atoms. The catalytic reduction of 4-nitrophenol to 4-aminophenol using NaBH4 in the presence of [Cu2(TDPH)4(QNX)].DMF, as catalyst was completed within 11 min. The 4-aminophenol product was confirmed using 1H NMR spectroscopy.
Highlights
Coordination polymers have attracted a lot of attention over the decades because of their interesting properties, synthetic routes and rich chemistry
12 Coordination polymers are usually prepared under conditions which allow for tunable structure and incorporation of building blocks with desired functions thereby making them suitable for specific purposes. 8 These class of compounds are characterized by large surface area and well-defined reaction environments which increases their potential applications in the area of heterogeneous catalysis
Elemental analysis of [Cu2(TDPH)4(QNX)].DMF conform with a mole ratio of 4:1:2 for 3,3-thiodipropionic acid, quinoxaline, and Cu(II) ion respectively, with one DMF molecule outside the coordination sphere
Summary
Coordination polymers have attracted a lot of attention over the decades because of their interesting properties, synthetic routes and rich chemistry. 2-6 Porous coordination polymers have evolved as a class of versatile and attractive functional porous materials They are made up of organic molecules connected by metal ions in a uniform porous network which incorporates sufficient stability and chemical resistance to most solvents. 8 These class of compounds are characterized by large surface area and well-defined reaction environments which increases their potential applications in the area of heterogeneous catalysis Chiral ligands such as 1,1’-bi-2-naphthol, porphyrins, and their derivatives have been used as building blocks in the preparation of coordination polymers for specific usage as asymmetric catalysts. The conjugated system of the quinoxaline ligand was exploited to incorporate additional luminescence property to the material along with the Cu(II) ion while the carboxylate linker was chosen to achieve a porous network structure. We report the synthesis, crystal structure, luminescence, and catalytic property of a coordination polymer assembled using Cu(II) ion, quinoxaline, and 3,3-thiodipropionic acid, and formulated as [Cu2(TDPH)4(QNX)].DMF. The rate of reduction process was followed with a UV-Vis spectrophotometer in the wavelength range of 250 – 600 nm
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