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.
Fritzsche, J., Denysenko, D., Grzywa, M. and Volkmer, D., 2017. CFA-13–a bifunctional perfluorinated metal–organic framework featuring active Cu (i) and Cu (ii) sites. Dalton Transactions, 46(43), pp.14907-14915.
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