K(I)-M(II) (M = Co, Mn) heterometallic-(perfluorinated) organic frameworks containing inorganic layered K–O–M linkages: synthesis, crystal structure, and magnetic properties

Abstract

Reactions of a perfluorinated ligand, tetrafluorophthalic acid (o-H₂BDC-F₄), with KNO₃ and M(OAc)₂ (M = Co, Mn) led to the formation of perfluorinated metal-organic frameworks [CoK₂(o-BDC-F₄)₂(MeOH)]_n (1) and [MnK₂(o-BDC-F₄)₂(DMF)]_n (2). The structures were characterized by elemental analyses, infrared spectra, and single-crystal X-ray diffraction. Both complexes show similar 2-D heterometallic-organic frameworks containing unusual layered inorganic K–O–M connectivities. For 1 and 2, ortho fluorines of o-BDC-F₄ are bound to the K(I) ion, while the other fluorines participate in the linkage of adjacent coordination layers forming 3-D supramolecular architectures via intermolecular FF interactions. Spectroscopic, thermal, and fluorescence properties have been investigated. Variable-temperature magnetic susceptibility studies indicate that 1 displays a weak antiferromagnetic effect between adjacent Co(II) ions.

Graphical abstract

Keywords:

• Heterometallic-organic framework
• Perfluorinated phthalate ligand
• Crystal structure
• Layered inorganic connectivity
• Magnetic property

Disclosure statement

No potential conflict of interest was reported by the authors.

Additional information

Funding

This work was supported by the National Natural Science Foundation of China [grant number 21201026]; the Nature Science Foundation of Jiangsu Province [grant number BK20131142]; a Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD).