Porous zinc and cobalt 2-nitroimidazolate frameworks with six-membered ring windows and a layered cobalt 2-nitroimidazolate polymorph
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Polymorphs of Zn(2-nIm)2 (compound 1 ) and Co(2-nIm)2 (compounds 2 and 3 ) (2-nIm = 2-nitroimidazole) have been prepared by two routes: solvothermal synthesis and recrystallisation of ZIF-65(Zn/Co). Compounds 1 and 2 are isostructural, with a tetrahedrally-connected framework topology related to, but different from, that of tridymite (lonsdaleite). Single crystal X-ray diffraction analysis showed that in compound 1 (Pccn, Z = 8; a = 8.462(8) Å, b = 14.549(15) Å, c = 18.799(18) Å, V = 2314(4) Å3) there is rotational disorder for two of the three crystallographically-distinct linker types, which has been investigated computationally and by solid-state NMR spectroscopy. Detailed adsorption studies on a sample of 1 prepared by recrystallisation show 1.1 mmol g-1 uptake of CO2 at 0.1 bar (25 °C) with high affinity for CO2 over CH4 and N2 (adsorption enthalpies of 39.5, 26.0 and 18.5 kJ mol-1, respectively). A cobalt analogue (compound 2 ) with improved water stability (but lower porosity) has also been prepared. Changing the conditions of synthesis and recrystallisation gives rise to a cobalt 2-nitroimidazolate (Co(2-nIm)2, compound 3 ), which has a layered structure (I41/amd, a = 6.025(18) Å, c = 26.95(8) Å, V = 978.3(5) Å3) containing sheets of tetrahedrally-connected Co2+ cations composed of four membered rings, without porosity.
Orsi , A , Price , D J , Kahr , J , Pillai , R S , Sneddon , S , Cao , S , Benoit , V , Łozińska , M M , Cordes , D B , Slawin , A M Z , Llewellyn , P L , Casely , I , Ashbrook , S E M , Maurin , G & Wright , P A 2017 , ' Porous zinc and cobalt 2-nitroimidazolate frameworks with six-membered ring windows and a layered cobalt 2-nitroimidazolate polymorph ' CrystEngComm , vol 19 , no. 10 , pp. 1377-1388 . DOI: 10.1039/C6CE02476A
© 2017 The Author(s). This work has been made available online in accordance with the publisher’s policies. This is the author created, accepted version manuscript following peer review and may differ slightly from the final published version. The final published version of this work is available at: https://doi.org/10.1039/C6CE02476A© 2017 The Author(s). This work has been made available online in accordance with the publisher’s policies. This is the author created, accepted version manuscript following peer review and may differ slightly from the final published version. The final published version of this work is available at: https://doi.org/10.1039/C6CE02476A
This work was supported by the European Community Seventh Framework Program (FP7/2007-2013) [grant agreement number 608490] (project M4CO2). A.O. would like to acknowledge the SCI for awarding a scholarship for her PhD research. G.M. thanks Institut Universitaire de France for its support. S.S. would like to thank the EPSRC for support EP/M506631/1. S.E.A would like to thank the Royal Society and Wolfson Foundation for a merit award.
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