Irreversible solvent-assisted structural transformation in 3D metal-organic frameworks: Structural modification and enhanced iodine-adsorption properties.

Abstract In this work, we demonstrate a solvent-assisted structural transformation between two 3D metal-organic frameworks (MOFs) ([Zn 4 ( α -bptc) 2 (H 2 O) 3 ] n ( 1 ) → {[Zn 2 ( α -bptc)(H 2 O) 4 ]·(pra)} n ( 2 )) ( α -H 4 bptc = 2,3,3′,4′-biphenyl tetra-carboxylic acid and pra = pyridin-2-amine) at room temperature by immersing complex 1 in a mother solution. The structural transformation involves not only solvent exchange but also the cleavage and formation of coordination bonds, which is confirmed by infrared spectroscopy, single-crystal X-ray diffraction analysis, powder X-ray diffraction patterns, and thermogravimetric analysis. Structural analyses revealed that significant modifications occurred during the transformation including the changes in lattice parameters, unit cell volume, space group, coordination number, secondary building units, and topological type. In the case of drastic structural transitions, significant changes in properties were also observed. Complex 2 displayed the interesting uptake and release of iodine with the changes in visible color, UV and fluorescence spectra, and fully reversible I2 uptake of 8.5 mg g−1, which further suggested about its future application as iodine absorbing material. Graphical Abstract Irreversible solvent-assisted structural transformation between two 3D Zn(II)-MOFs. Unlabelled Image Highlights • A Zn(II) compound 2 based on α -H 4 bptc is synthesized and fully characterized. • Irreversible solvent-assisted structural transformation between two 3D Zn(II)-MOFs. • The transformation is accomplished by coordination bond cleavage and formation. • Complex 2 displays reversible I 2 uptake with visible color change. [ABSTRACT FROM AUTHOR]