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Issue 40, 2016
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Flexible chiral pyrazolate-based metal–organic framework containing saddle-type CuI4(pyrazolate)4 units

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Abstract

The syntheses and crystal structures of [CuI2(phbpz)]·MeOH (lp-CFA-9, lp = large-pore) and [CuI2(phbpz)] (np-CFA-9, np = narrow-pore; H2-phbpz = 3,3′,5,5′-tetraphenyl-1H,1′H-4,4′-bipyrazole) are described. The copper(I)-containing metal–organic framework (termed [C with combining low line]oordination [F with combining low line]ramework [A with combining low line]ugsburg University-9, lp-CFA-9) crystallizes in the trigonal crystal system, within the chiral space group P3221 (no. 154) and with the following unit cell parameters: a =18.2348(6), c = 16.3950(4) Å, and V = 4721.1(2) Å3. Lp-CFA-9 features a 3-D microporous framework structure of Cu4pz4 (pz = pyrazolate) SBUs with the D2d (= [4 with combining macron]2m) symmetry connected by single bonds creating one-dimensional channels expanding in the c-direction of the crystal lattice. The framework flexibility of CFA-9 has been demonstrated by single-crystal and powder X-ray analyses as well as by sorption measurements. CFA-9 exhibits weak binding of carbon monoxide on Cu(I) centers. The reactivity of CFA-9 towards oxidizing agents, such as H2O2, t-BuOOH and Br2 was also investigated. Additionally, CFA-9 shows luminescence upon exposure to UV radiation.

Graphical abstract: Flexible chiral pyrazolate-based metal–organic framework containing saddle-type CuI4(pyrazolate)4 units

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Publication details

The article was received on 20 Jul 2016, accepted on 12 Sep 2016 and first published on 13 Sep 2016


Article type: Paper
DOI: 10.1039/C6CE01594H
Citation: CrystEngComm, 2016,18, 7883-7893
  • Open access: Creative Commons BY license
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    Flexible chiral pyrazolate-based metal–organic framework containing saddle-type CuI4(pyrazolate)4 units

    M. Grzywa, D. Denysenko, A. Schaller, A. Kalytta-Mewes and D. Volkmer, CrystEngComm, 2016, 18, 7883
    DOI: 10.1039/C6CE01594H

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