hrvatski jezikClear Cookie - decide language by browser settings

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

PDF - Accepted Version - article
Download (808kB) | Preview


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
Project titleProject leaderProject codeProject type
Mehaniokemijska reaktivnost pod kontroliranim uvjetima temperature i atmosfere za čišću sintezu funkcionalnih materijala-MECHANOCONTROLKrunoslav UžarevićUIP-2014-09-4744HRZZ
Mechanochemical and solvent-free strategies towards functional porous materials with advanced physico-chemical and catalytic propertiesKrunoslav UžarevićPZS-2019-02-4129ESF
Studija važnosti spinskih međudjelovanja kao osnova za nove pristupe u istraživanju materijala-SPESMarina Ilakovac KvederIP-2018-01-3168HRZZ
Mechanochemistry for Sustainable IndustryCOST Association EUCA18112EC
Depositing User: Krunoslav Užarević
Date Deposited: 14 Dec 2020 12:10
DOI: 10.1021/jacs.9b10251

Actions (login required)

View Item View Item


Downloads per month over past year

Increase Font
Decrease Font
Dyslexic Font