Bonding investigation on d, f-block coordination compounds by combining density functional calculations with Mssbauer spectroscopic parameters

Kaneko, Masashi   

This study aims to perform the optimization of density functional methods using experimental data of Mssbauer isomer shifts and apply these methods to d, f-block coordination chemistry. In the d-block complexes, the validity for the spin-crossover (SCO) switching behavior of iron(II) assembled complexes was confirmed. The application of this method indicated that whether SCO occurs or not depends on the dihedral angle between iron atom and pyridine plane. In the f-block complexes, the benchmarking of computational method was performed using Eu and Np Mssbauer isomer shifts. The optimized method reproduced the separation behavior of Am(III) ion from Eu(III) ion and implied that the difference in the bonding contribution between 5f(Am) and 4f(Eu) attributes to the selectivity of Am(III) compared with Eu(III).