Issue 43, 2017

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

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

Supplementary files

Article information

Article type
Paper
Submitted
11 Jul 2017
Accepted
12 Oct 2017
First published
12 Oct 2017

Dalton Trans., 2017,46, 14907-14915

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, 46, 14907 DOI: 10.1039/C7DT02512B

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