Electronic Structure and d–d Spectrum of Metal–Organic Frameworks with Transition-Metal Ions

Popov, Ilya; Raenko, Dmitrii; Tchougréeff, Andrei; Besley, Elena

Abstract

The electronic structure of metal–organic frameworks (MOFs) containing transition metal (TM) ions represents a significant and largely unresolved computational challenge due to limited solutions to the quantitative description of low-energy excitations in open d-shells. These excitations underpin the magnetic and sensing properties of TM MOFs, including the observed remarkable spin-crossover phenomenon. We introduce the effective Hamiltonian of crystal field approach to study the d–d spectrum of MOFs containing TM ions; this is a hybrid QM/QM method based on the separation of crystal structure into d- and s,p-subsystems treated at different levels of theory. We test the method on model frameworks, carbodiimides, and hydrocyanamides and a series of M-MOF-74 (M = Fe, Co, Ni) and compare the computational predictions to experimental data on magnetic properties and Mössbauer spectra.

Citation

Popov, I., Raenko, D., Tchougréeff, A., & Besley, E. (2023). Electronic Structure and d–d Spectrum of Metal–Organic Frameworks with Transition-Metal Ions. Journal of Physical Chemistry C, 127(44), 21749–21757. https://doi.org/10.1021/acs.jpcc.3c05025

• Journal Article Type: Article
• Acceptance Date: Oct 11, 2023
• Online Publication Date: Oct 27, 2023
• Publication Date: Oct 27, 2023
• Deposit Date: Oct 28, 2023
• Publicly Available Date: Oct 30, 2023
• Journal: Journal of Physical Chemistry C
• Print ISSN: 1932-7447
• Electronic ISSN: 1932-7455
• Publisher: American Chemical Society
• Peer Reviewed: Peer Reviewed
• Volume: 127
• Issue: 44
• Pages: 21749–21757
• DOI: https://doi.org/10.1021/acs.jpcc.3c05025
• Keywords: Electronic structure, Energy, Group theory, Metal organic frameworks, Quantum mechanics
• Public URL: https://nottingham-repository.worktribe.com/output/26537516
• Publisher URL: https://pubs.acs.org/doi/10.1021/acs.jpcc.3c05025