The Impact of Linker Disorder in Multivariate Metal-Organic Frameworks on Mechanical and Phonon Properties
- 1Center for Molecular Modeling, Ghent University, Technologiepark 46, Zwijnaarde, Belgium, 9052
- 2Nanochemistry Department, Max Planck Institute for Solid State Research, Heisenbergstrasse 1, Stuttgart, Germany, 70569
- 3Institute of Inorganic Chemistry II, Ulm University, Albert-Einstein-Allee 11, Ulm, Germany, 89081
Abstract
While the reticular nature of metal-organic frameworks (MOFs) allows incorporating highly symmetric building blocks, it also supports linker asymmetry and linker mixing within a single material. These imperfections impact both the framework structure and, crucially, its underlying physical properties. However, microscopic configurations of organic linkers are challenging to detect experimentally and we lack accurate atomistic models computationally. This work investigates the impact of orientational and compositional linker disorder on the emergent macroscopic behaviour of UiO-type MOFs with asymmetric linkers, based on azobenzene and stilbene compounds with different mixedlinker compositions. Atomic interactions in these multivariate MOFs are modelled using an accurate machine-learning potential (MLP) derived with a recent cluster-based learning algorithm. We find that axial linker rotations occur below the millisecond time scale and are hindered for asymmetric linkers, thereby leading to geometric frustration of the linker backbone within the cubic crystal system of the MOF. Flat bands in the phonon band structures corroborate the latter effect. We predict bulk moduli of a series of mono- and multivariate Zr-MOFs and uncover a nonlinear trend with linker composition. This work demonstrates that individual structural models fail to capture the complexity of realistic MOFs with mixed-linker compositions, and a structural ensemble approach is necessary to estimate representative properties. Combining an ensemble description with accurate MLPs holds promise to more generally model spatially disordered framework materials with multiple linkers and establish novel structure-function relationships.
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BibTeX
@misc{dobbelaere2026impact,
title = {{The Impact of Linker Disorder in Multivariate Metal-Organic Frameworks on Mechanical and Phonon Properties}},
author = {Pieter Dobbelaere and Wim Temmerman and Ardeshir Dadgar Yeganeh and Simon Krause and Veronique Van Speybroeck},
howpublished = {ChemRxiv},
year = {2026},
month = oct,
doi = {10.26434/chemrxiv.15010311/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010311/v1},
note = {CC BY},
}
RIS
TY - UNPB
TI - The Impact of Linker Disorder in Multivariate Metal-Organic Frameworks on Mechanical and Phonon Properties
AU - Pieter Dobbelaere
AU - Wim Temmerman
AU - Ardeshir Dadgar Yeganeh
AU - Simon Krause
AU - Veronique Van Speybroeck
PY - 2026
DA - 2026/10/12
PB - ChemRxiv
DO - 10.26434/chemrxiv.15010311/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010311/v1
AB - While the reticular nature of metal-organic frameworks (MOFs) allows incorporating highly symmetric building blocks, it also supports linker asymmetry and linker mixing within a single material. These imperfections impact both the framework structure and, crucially, its underlying physical properties. However, microscopic configurations of organic linkers are challenging to detect experimentally and we lack accurate atomistic models computationally. This work investigates the impact of orientational and compositional linker disorder on the emergent macroscopic behaviour of UiO-type MOFs with asymmetric linkers, based on azobenzene and stilbene compounds with different mixedlinker compositions. Atomic interactions in these multivariate MOFs are modelled using an accurate machine-learning potential (MLP) derived with a recent cluster-based learning algorithm. We find that axial linker rotations occur below the millisecond time scale and are hindered for asymmetric linkers, thereby leading to geometric frustration of the linker backbone within the cubic crystal system of the MOF. Flat bands in the phonon band structures corroborate the latter effect. We predict bulk moduli of a series of mono- and multivariate Zr-MOFs and uncover a nonlinear trend with linker composition. This work demonstrates that individual structural models fail to capture the complexity of realistic MOFs with mixed-linker compositions, and a structural ensemble approach is necessary to estimate representative properties. Combining an ensemble description with accurate MLPs holds promise to more generally model spatially disordered framework materials with multiple linkers and establish novel structure-function relationships.
ER -