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CFA-13 – a bifunctional perfluorinated metal–organic framework featuring active Cu(I) and Cu(II) sites

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Abstract

The synthesis and crystal structure of the mixed-valent perfluorinated metal–organic framework (Me2NH2)[CFA-13] (Coordination Framework Augsburg University-13), (Me2NH2)[CuI3CuII2(tfpc)4] (H2-tfpc = 3,5-bis(trifluoromethyl)-1H-pyrazole-4-carboxylic acid) is described. The copper-containing MOF crystallizes in the monoclinic crystal system within the space group P21/n (no. 14) and the unit cell parameters are as follows: a = 22.3887(19), b = 13.6888(8), c = 21.1804(13) Å, β = 90.495(3)°, V = 6491.0(8) Å3. (Me2NH2)[CFA-13] features a porous 3-D structure constructed from two types of secondary building units (SBUs). Besides novel trinuclear [CuI3(pz)4] coordination units, the network also exhibits Cu(II) paddle-wheel SBUs. (Me2NH2)[CFA-13] is fully characterized by single crystal X-ray diffraction, thermogravimetric analysis, variable temperature powder X-ray diffraction, IR spectroscopy, photoluminescence, gas sorption measurements and pulse chemisorption experiments. M[CFA-13] (M = K+, Cs+) frameworks were prepared by postsynthetic exchange of interchannel dimethylammonium cations. Moreover, it was shown that CO molecules can be selectively bound at Cu(I) sites of [CuI3(pz)4] units, whereas Cu(II) paddle-wheel units bind selectively NH3 molecules.

Graphical abstract: CFA-13 – a bifunctional perfluorinated metal–organic framework featuring active Cu(i) and Cu(ii) sites

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Publication details

The article was received on 11 Jul 2017, accepted on 12 Oct 2017 and first published on 12 Oct 2017


Article type: Paper
DOI: 10.1039/C7DT02512B
Citation: Dalton Trans., 2017, Advance Article
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    CFA-13 – a bifunctional perfluorinated metal–organic framework featuring active Cu(I) and Cu(II) sites

    J. Fritzsche, D. Denysenko, M. Grzywa and D. Volkmer, Dalton Trans., 2017, Advance Article , DOI: 10.1039/C7DT02512B

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