Electronic structure of the [Ni(Salen)] complex studied by core-level spectroscopies

The nature and structure of occupied and empty valence electronic states (molecular orbitals, MOs) of the [Ni(Salen)] molecular complex (NiO2N2C16H14) have been studied by X-ray photoemission and absorption spectroscopy combined with density functional theory (DFT) calculations. As a result, the composition of the high-lying occupied and low-lying unoccupied electronic states has been identified. In particular, the highest occupied molecular orbital (HOMO) of the complex is found to be predominantly located on the phenyl rings of the salen ligand, while the states associated with the occupied Ni 3d-derived molecular orbitals (MOs) are at higher binding energies. The lowest unoccupied molecular orbital (LUMO) is also located on the salen ligand and is formed by the 2p pi orbitals of carbon atoms in phenyl groups of the salen macrocycle. The unoccupied MOs above the LUMO reflect sigma- and pi-bonding between Ni and its nearest neighbours. All valence states have highly mixed character. The specific nature of the unoccupied Ni 3d-derived sigma-MO is a consequence of donor-acceptor chemical bonding in [Ni(Salen)].

Automated summary

Through X-ray photoemission and absorption spectroscopy combined with DFT calculations, the nature and structure of occupied and empty valence electronic states of the [Ni(Salen)] molecular complex have been studied, identifying the composition of high-lying occupied and low-lying unoccupied electronic states. The HOMO of the complex is mainly located on the phenyl rings of the salen ligand, while the states associated with the occupied Ni 3d-derived MOs are at higher binding energies, and the LUMO is located on the salen ligand and formed by the carbon atoms in phenyl groups.