title: Zeolitic imidazolate framework-71 nanocrystals and a novel SOD-type polymorph: solution mediated phase transformations, phase selection via coordination modulation and a density functional theory derived energy landscape.
abstract: We report a rapid additive-free synthesis of nanocrystals (NCs) of RHO-type ZIF-71 () of composition [Zn(dcim)2] (dcim = 4,5-dichloroimidazolate) in 1-propanol as solvent at room temperature. NC- has a size of 30-60 nm and exhibits permanent microporosity with a surface area (SBET = 970 m(2) g(-1)) comparable to that of microcrystalline material. When kept under the mother solution NC- undergoes transformation into a novel SOD-type polymorph (), which in turn converts into known ZIF-72 () with lcs topology. It is shown that microcrystals (MCs) of can be favourably synthesised using 1-methylimidazole as a coordination modulator. NC- with size <200 nm was prepared using NC-ZIF-8 as a template with SOD topology in a solvent assisted ligand exchange-related process. DFT-assisted Rietveld analysis of powder XRD data revealed that novel polymorph possesses an unusual SOD framework conformation. was further characterised with regard to microporosity (SBET = 597 m(2) g(-1)) and thermal as well as chemical stability. DFT calculations were performed to search for further potentially existing but not-yet synthesised polymorphs in the [Zn(dcim)2] system.
authors.affiliation: Institut für Anorganische Chemie, Leibniz Universität Hannover, Callinstrasse 9, 30167 Hannover, Germany. Michael.Wiebcke@acb.uni-hannover.de.
authors.forename: Maria E
authors.initials: ME
authors.lastname: Schweinefuss
authors.forename: Sergej
authors.initials: S
authors.lastname: Springer
authors.forename: Igor A
authors.initials: IA
authors.lastname: Baburin
authors.forename: Todor
authors.initials: T
authors.lastname: Hikov
authors.forename: Klaus
authors.initials: K
authors.lastname: Huber
authors.forename: Stefano
authors.initials: S
authors.lastname: Leoni
authors.forename: Michael
authors.initials: M
authors.lastname: Wiebcke