Metal-organic frameworks (MOFs) are advanced 3-dimensional, highly porous coordination polymers which consist of metal cations and anions of organic functional groups aka “linkers”. Most MOFs are solids which can act as chemical matrices for controlled sorption, desorption of molecules in gas and liquid phase, and chemo-sensing. Aluminum MOFs (Al-MOFs) are special among MOFs as they have both high chemical and thermal stability and significant structural diversity to accommodate various adsorbate molecules, including hazardous compounds. Porphyrins are large-ring nitrogen heterocyclic compounds with high versatility of structure and properties, which were extensively studied for sensing various small molecules and ions, and as photosensitizers. We describe chemical synthesis of Al-MOFs based on meso-tetra(4-carboxyphenyl)porphine TCPP. These compounds are denoted Al-MOF-H2TCPP and Al-MOF-MeTCPP and they can contain transition metal cations (Me = Cu, Zn, Ni) in the porphyrin ring. Synthetic pathways notably include the one-step (direct) preparation of Al-MOF-MeTCPP, and a two-step route. Further, we report the controlled, step-wise purification and activation of the obtained Al-MOFs to remove precursors and solvents used in the synthetic procedure. The purity of the obtained Al-MOF compounds is checked by the complementary ATR-FTIR spectroscopy and powder XRD. Further, we provide the previously not available, detailed assignments of peaks in vibrational spectra of the obtained Al-MOFs. Assignments are based on model compounds of two classes, small-molecule “building blocks” and Al-MOFs of simpler structure, and the literature. Novel high-purity Al-MOFs based on TCPP are attractive candidates as sorbents for selective removal of environmental contaminants and hazardous compounds in gaseous and liquid phase, and potential optical chemo-sensors.

Synthesis, purification, and characterization of aluminum metal-organic frameworks based on TCPP porphyrin

ACS Spring Meeting 2021

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