Issue 40, 2016

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

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

Supplementary files

Article information

Article type
Paper
Submitted
20 Jul 2016
Accepted
12 Sep 2016
First published
13 Sep 2016
This article is Open Access
Creative Commons BY license

CrystEngComm, 2016,18, 7883-7893

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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