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Large Breathing Effect Induced by Water Sorption in the Exceptionally Stable Nonporous Non-MOF Crystalline Material

preprint
submitted on 26.01.2021, 13:29 and posted on 28.01.2021, 07:10 by Michał Magott, Bartłomiej Gaweł, Marcin Sarewicz, Mateusz Reczyński, Karolina Ogorzały, Wacław Makowski, Dawid Pinkowicz
We report a non-MOF crystalline material {[Mn(imH)]2[Mo(CN)8]}n (imH = imidazole) with exceptional water sorption properties and a very large breathing effect accompanied by an outstanding stability and cyclability – properties that are absolutely unique for this class of compounds (Prussian Blue Analogs). Some previously published PBAs indeed show some sorption properties, but their cyclability is extremely limited - usually 1-3 cycles - followed by significant decomposition/amorphization. Our compound can be cycled more than 50 times without any fatigue and the sorption/desorption proceeds through four different crystal phases, which we have fully characterized structurally enabling the complete understanding of the sorption and breathing mechanism in this material - an achievement rarely reported for MOFs or PBAs.
The unique structure of {[Mn(imH)]2[Mo(CN)8]}n enables very strong coupling of its exceptional water sorption performance with the magnetic and photomagnetic properties of the framework, e.g. the sorption process can be followed by in-situ EPR spectroscopy with huge changes in the EPR signal intensity depending on the hydration level.

Funding

Quantum nanomagnets based on metal complexes with unusual geometry and the use of new, non-standard ligands.

National Science Center

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Rational design and synthesis of magnetic porous coordination polymers and molecular multiferroics.

Ministry of Science and Higher Education

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Kwazi-equilibrium thermodesorption as a new method of testing water adsorption in porous coordination polymers and their hydrothermal stability

National Science Center

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History

Email Address of Submitting Author

dawid.pinkowicz@uj.edu.pl

Institution

Jagiellonian University, Faculty of Chemistry

Country

Poland

ORCID For Submitting Author

0000-0002-9958-3116

Declaration of Conflict of Interest

No conflicts to declare

Version Notes

Version 1.0 after internal review and before submission to a scientific journal.

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