Controlling the Polymorphism and Topology Transformation in Porphyrinic Zirconium Metal–Organic Frameworks via Mechanochemistry

Karadeniz, Bahar; Žilić, Dijana; Huskić, Igor; Germann, Luzia S.; Fidelli, Athena M.; Muratović, Senada; Lončarić, Ivor; Etter, Martin; Dinnebier, Robert E.; Barišić, Dajana; Cindro, Nikola; Islamoglu, Timur; Farha, Omar K.; Friščić, Tomislav; Užarević, Krunoslav (2019) Controlling the Polymorphism and Topology Transformation in Porphyrinic Zirconium Metal–Organic Frameworks via Mechanochemistry. Journal of the American Chemical Society, 141 (49). pp. 19214-19220. ISSN 0002-7863

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Official URL: https://pubs.acs.org/doi/10.1021/jacs.9b10251

Abstract

Tetratopic porphyrin-based metal–organic frameworks (MOFs) represent a particularly interesting subclass of zirconium MOFs due to the occurrence of several divergent topologies. 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, obtaining pure hexagonal PCN-223 and cubic MOF-525 phases in 20–60 min of milling. The reactions are mainly governed by the milling additives and the zirconium precursor. In situ monitoring by synchrotron powder X-ray diffraction revealed that specific reaction conditions resulted in the formation of MOF-525 as an intermediate, which rapidly converted to PCN-223 upon milling. Electron spin resonance 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.

Item Type:

Article

Uncontrolled Keywords:

Mechanochemical synthesis; MOFs, Additives; Oxides, Polymorphism; Metal-organic frameworks; Mathematical methods; MOF-525, PCN-223

Subjects:

NATURAL SCIENCES > Chemistry > Physical Chemistry
NATURAL SCIENCES > Chemistry > Inorganic Chemistry

Divisions:

Division of Physical Chemistry

Projects:

Project title	Project leader	Project code	Project type
Mehaniokemijska reaktivnost pod kontroliranim uvjetima temperature i atmosfere za čišću sintezu funkcionalnih materijala-MECHANOCONTROL	Krunoslav Užarević	UIP-2014-09-4744	HRZZ
Mechanochemical and solvent-free strategies towards functional porous materials with advanced physico-chemical and catalytic properties	Krunoslav Užarević	PZS-2019-02-4129	ESF
Studija važnosti spinskih međudjelovanja kao osnova za nove pristupe u istraživanju materijala-SPES	Marina Ilakovac Kveder	IP-2018-01-3168	HRZZ
Mechanochemistry for Sustainable Industry	COST Association EU	CA18112	EC