Exploring the interplay between ligand and topology in zeolitic imidazolate frameworks with computational chemistry

Abstract

Exploring the interplay between ligand and topology in zeolitic imidazolate frameworks with computational chemistry, Molecular Simulation, 40:1-3, 25-32,In this paper, we briefly describe recent computational studies related to the exploration and understanding of the complex energy landscape of zeolitic imidazolate frameworks (ZIFs), including zinc-based and lithium boron-based ZIFs. This rich and vast landscape can be usefully navigated with the aid of computational chemistry, by studying existing crystal structures and screening hypothetical structures selected for their potentially interesting topologies. Energy -density trends are discussed, together with the key role of linker-linker interactions.

Experimental and Theoretical Evaluation of the Stability of True MOF Polymorphs Explains Their Mechanochemical Interconversions

“…76,77 While functionals tailored to reproduce van der Waals forces have been developed 78,79 and applied to ZIF systems, 80 a more widely adopted approach for modelling them remains the semi-empirical dispersion correction (SEDC) in combination with one of the available general gradient approximation (GGA) or hybrid functionals. 65,81 Dispersion-corrected DFT has been applied to ZIFs based on both non-substituted 79 and substituted 83,84 imidazoles, showing improved energy rankings compared to uncorrected DFT calculations. 39 Nonetheless, polymorphic structures of Zn(MeIm)2 and Zn(EtIm) 2 have not yet been comprehensively analyzed with dispersion-corrected DFT.…”

Computational evaluation of metal pentazolate frameworks: inorganic analogues of azolate metal–organic frameworks

“… 34 , 47 – 50 It is therefore important to compensate for the poor description of van der Waals interactions by utilizing functionals tailored for accurately reproducing long-range van der Waals interactions, 51 , 52 symmetry-adapted perturbation theory (SAPT-DFT) 53 approaches, or semi-empirical dispersion corrections (SEDC). 46 , 54 – 56 Such dispersion-corrected DFT calculations were shown to improve energy rankings of ZIFs 28 , 57 , 58 in comparison to plain DFT calculations. 59 …”

Thermal and mechanical stability of zeolitic imidazolate frameworks polymorphs

“…function of metal and linker modifications, 35,36 its predictive power is limited because it addresses only one of the key criteria for stability of a material.…”