Impact of Ligand Substitution and Metal Node Exchange in the Electronic Properties of Scandium Terephthalate Frameworks.

The search for sustainable alternatives to established materials is a sensitive topic in materials science. Due to their unique structural and physical characteristics, the composition of metal-organic frameworks (MOFs) can be tuned by the exchange of metal nodes and the functionalization of organic ligands, giving rise to a large configurational space. Considering the case of scandium terephthalate MOFs and adopting an automatized computational framework based on density-functional theory, we explore the impact of metal substitution with the earth-abundant isoelectronic elements Al and Y, and ligand functionalization of varying electronegativity. We find that structural properties are strongly impacted by metal ion substitution and only moderately by ligand functionalization. In contrast, the energetic stability, the charge density distribution, and the electronic properties, including the size of the band gap, are primarily affected by the termination of the linker molecules. Functional groups such as OH and NH2 lead to particularly stable structures thanks to the formation of hydrogen bonds and affect the electronic structure of the MOFs by introducing midgap states.

Electronic Structure and Core Spectroscopy of Scandium Fluoride Polymorphs.

Microscopic knowledge of the structural, energetic, and electronic properties of scandium fluoride is still incomplete despite the relevance of this material as an intermediate for the manufacturing of Al-Sc alloys. In a work based on first-principles calculations and X-ray spectroscopy, we assess the stability and electronic structure of six computationally predicted ScF3 polymorphs, two of which correspond to experimentally resolved single-crystal phases. In the theoretical analysis based on density functional theory (DFT), we identify similarities among the polymorphs based on their formation energies, charge-density distribution, and electronic properties (band gaps and density of states). We find striking analogies between the results obtained for the low- and high-temperature phases of the material, indirectly confirming that the transition occurring between them mainly consists of a rigid rotation of the lattice. With this knowledge, we examine the X-ray absorption spectra from the Sc and F K-edge contrasting first-principles results obtained from the solution of the Bethe-Salpeter equation on top of all-electron DFT with high-energy-resolution fluorescence detection measurements. Analysis of the computational results sheds light on the electronic origin of the absorption maxima and provides information on the prominent excitonic effects that characterize all spectra. A comparison with measurements confirms that the sample is mainly composed of the high- and low-temperature polymorphs of ScF3. However, some fine details in the experimental results suggest that the probed powder sample may contain defects and/or residual traces of metastable polymorphs.