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

Autori
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

Izvornik
Journal of the American Chemical Society (0002-7863) 141 (2019), 49; 19214-19120

Vrsta, podvrsta i kategorija rada
Radovi u časopisima, članak, znanstveni

Ključne riječi
Mechanochemistry ; zirconium MOFs ; porphyrin linker ; spin qubits, polymorphism ; polymorph resolution ; in situ monitoring ; direct transformation of MOFs
(Mechanochemistry ; zirconium MOFs ; porphyrin linker ; spin qubits ; polymorphism ; polymorph resolution ; in situ monitoring ; direct transformation of MOFs)

Sažetak
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.

Izvorni jezik
Engleski

Znanstvena područja
Kemija

POVEZANOST RADA