A theoretical study of structure properties and stability in different ligands coordinated Cu-MOFs.

A comprehensively theoretical study of structural properties and thermostability is performed to investigate the role of ligands in Metal Organic Frameworks (MOFs). By fitting the experimental EPR spectra, the high order perturbation formulae of a 3 d9 ion in four Cu-MOFs with ligands btm, bte, btp and btb are adopted for orthorhombically and tetragonally elongated octahedral [CuO 2 N 4 ]12− groups so as to reveal the local environment around central Cu2+, including the detail structure information and local electromagnetic properties. Since the application of MOFs are normally limited by the unsatisfied thermostability, the molecule dynamic (MD) calculation based on density functional theory (DFT) is performed to clarify the influence on the stability of MOFs from the different ligands. Based on the above investigations, the mechanism of ligands substitution in MOFs can be comprehensively understood, which would be useful for designing and synthesizing novel MOFs. • EPR parameters of different ligans coordinated MOFs are studied. • M 2 (and M 3) and M 1 (and M 4) show orthorhombical and tetragonal elongation. • M 1 is the best one when considering the local environment of Cu2+. • Ligands substitution can modify the structure distortion of the active sites. [ABSTRACT FROM AUTHOR]