Controlling the polymorphism and topology transformation in porphyrinic zirconium metal-organic frameworks via mechanochemistry.

Author(s) Karadeniz, B.; Žilić, D.; Huskic, I.; Germann, L.Silvana; Fidelli, A.M.; Muratovic, S.; Lončarić, I.; Etter, M.; Dinnebier, R.E.; Barišić, D.; Cindro, N.; Islamoglu, T.; Farha, O.K.; Friščić, T.; Užarević, K.
Journal J Am Chem Soc
Date Published 2019 Nov 20
Abstract

Tetratopic porphyrin-based MOFs represent a particularly interesting subclass of zirconium MOFs due to the occurrence of several divergent topologies. The control over the target topology is a demanding task and reports often show products containing phase contamination. We demonstrate how mechanochemistry can be exploited for controlling the polymorphism in 12-coordinated porphyrinic zirconium MOFs, gaining pure hexagonal () PCN-223 and cubic () MOF-525 phases in 20-60 minutes of milling. The reactions are mainly governed by the milling additives and the zirconium precursor. In situ monitoring by synchrotron powder X-ray diffraction (PXRD) revealed that specific reaction conditions resulted in the formation of MOF-525 as an intermediate, which rapidly convert-ed to PCN-223 upon milling. Electron spin resonance (ESR) measurements revealed significant differences between the spectra of paramagnetic centers in two polymorphs, showing a potential of polymorphic Zr-MOFs as tunable supports in spintronics applications.

DOI 10.1021/jacs.9b10251
ISSN 1520-5126
Citation Karadeniz B, Žilić D, Huskic I, Germann LS, Fidelli AM, Muratovic S, et al. Controlling the polymorphism and topology transformation in porphyrinic zirconium metal-organic frameworks via mechanochemistry. J Am Chem Soc. 2019.