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Electronic Structure and d-d Spectrum of Metal-Organic Frameworks with Transition-Metal Ions
Ilya Popov1, Dmitrii Raenko2, Andrei Tchougréeff2
1School of Chemistry, University of Nottingham, University Park, Nottingham NG7 2RD, U.K.
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.
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