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Controllable synthesis and transformations of magnetic porphyrin-based zirconium MOFs and MOF composites by mechanochemistry

Metal-organic frameworks are porous crystalline materials built from metal nodes bridged by organic linkers. Porphyrins, a group of heterocyclic macromolecules with a large π-aromatic system, are particularly attractive linkers for MOF formation. Various metals can be coordinated to the center of porphyrin to create single-cation metalloporphyrins with advanced electrochemical and photophysical properties. Including porphyrins as building units of MOFs widens the potential application area of both the MOFs and porphyrins. Herein we present the liquid-assisted mechanochemical synthesis of various metalloporphyrin-based metal-organic frameworks. In-situ synchrotron PXRD monitoring has been carried out to demonstrate kinetic and mechanistic details of milling reactions. That data was used to tune the reaction conditions toward the target topologies.1 Continuous-wave and pulsed electron paramagnetic resonance spectroscopy (EPR) at X-band were applied in order to analyze the potential of metalloporphyrin-based MOFs as electron spin qubit candidates. Additionally, we will present here the encapsulation of fullerene C60 into the copper porphyrin MOFs by one-pot mechanochemical reactions, and its effect on the magnetic properties of metalloporphyrin zirconium MOF, C60@Cu0.1PCN223.

MOFs, Mechanochemistry, EPR

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