2024/02/12 by Joshua Edzards, Holger‐Dietrich Saßnick, Holger-Dietrich Saßnick +7 · 1 voice · 2 citations
Chemistry · Engineering · Materials Science · Physics and Astronomy · #Chemical engineering #Chemistry #Combinatorial chemistry #Computer science #Engineering #FOS: Physical sciences #Linker #Magnetism in coordination complexes #Materials Science (cond-mat.mtrl-sci) #Materials science #Metal #Metal-Organic Frameworks: Synthesis and Applications #Nanotechnology #Organic and Molecular Conductors Research #Organic chemistry #Substitution (logic) #Surface modification #cond-mat.mtrl-sci
paper · pdf · doi:10.48550/arxiv.2402.07733
openalex publication_date 2024/02/12 · arxiv published 2024/02/12 · arxiv updated 2024/02/12 · openalex created_date 2024/02/14 · openalex updated_date 2026/08/01
The chemical flexibility of metal-organic frameworks (MOFs) offers an ideal platform to tune structure and composition for specific applications, from gas sensing to catalysis and from photoelectric conversion to energy storage. This variability gives rise to a large configurational space that can be efficiently explored using high-throughput computational methods. In this work, we investigate from first principles the structural and electronic properties of MOF-5 variants obtained by replacing Zn with Be, Mg, Cd, Ca, Sr, and Ba, and by functionalizing the originally H-passivated linkers with CH3, NO2, Cl, Br, NH2, OH, and COOH groups. To build and analyze the resulting 56 structures, we employ density-functional theory calculations embedded in an in-house developed library for automatized calculations. Our findings reveal that structural properties are mainly defined by metal atoms and large functional groups which distort the lattice and modify coordination. Stability is largely influenced by functionalization and enhanced by COOH and OH groups which promote the formation of hydrogen bonds. The charge distribution within the linker is especially influenced by functional groups with electron-withdrawing character while the metal nodes play a minor role. Likewise, the band-gap size is crucially determined by ligand functionalization. The smallest gaps are found with NH2 and OH groups which introduce localized orbitals at the top of the valence band. This characteristic makes these functionalizations particularly promising for the design of MOF-5 variants with enhanced gas uptake and sensing properties.