Jump to main content
Jump to site search

Issue 45, 2013
Previous Article Next Article

Impact of functionalized linkers on the energy landscape of ZIFs

Author affiliations

Abstract

Zeolitic imidazolate frameworks (ZIFs) are well-known for their thermal and chemical stability, as well as for their structural diversity reminiscent of those found in the realm of zeolites. Linker–linker interactions were recognized as essential in the discovery of new topologies through the choice of substituted imidazolates. However, the impact of the linker through modification of the imidazolate's substituents on the energy landscape of ZIFs remains to be rationalized. In this work, LiB-based ZIFs serve as model crystal structures to explore the impact of linker–linker interactions, varying the number and position of methyl groups. The study focuses on the characteristics of experimental and hypothetical structures studied by first principle DFT-D calculations, and further interpreted through QSPR and Non covalent interaction (NCI) analysis. We provide an empirical QSPR model accounting for linker and topology effects on the stability of the frameworks. Both the position and number of substituents on the imidazolate linkers have a profound impact on the energy landscape of ZIFs, reshuffling the ranking of stabilized versus less stable topologies that were otherwise almost isoenergetic with unsubstituted imidazolate. NCI analysis revealed that methyl substituents induce repulsive interactions within the boron-centred cluster that are compensated by attractive non-bonded interactions at the larger scale of the solid. Besides the kinetic factors at play in ZIF synthesis which are difficult to consider from a modelling perspective, our calculations show that thermodynamic considerations are at work, explaining the intractability of certain topologies with certain linkers. Our calculations provide insight into the magnitude of the thermodynamic penalties that must be overcome in order to form particular topologies and the energy scale that needs to be overcome to generate lower density materials – a target for many experimental groups. The identified dominant linker–linker interactions could be exploited to overcome the limitations of current synthesis techniques.

Graphical abstract: Impact of functionalized linkers on the energy landscape of ZIFs

Back to tab navigation

Supplementary files

Article information


Submitted
11 Jun 2013
Accepted
05 Aug 2013
First published
06 Aug 2013

CrystEngComm, 2013,15, 9603-9612
Article type
Paper

Impact of functionalized linkers on the energy landscape of ZIFs

R. Galvelis, B. Slater, R. Chaudret, B. Creton, C. Nieto-Draghi and C. Mellot-Draznieks, CrystEngComm, 2013, 15, 9603 DOI: 10.1039/C3CE41103F

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.


Social activity

Search articles by author

Spotlight

Advertisements