Svirskiy Gleb I, Generalov Alexander V, Vinogradov Nikolay A, Brykalova Xenia O, Vereshchagin Anatoly V, Levin Oleg V, Lyalin Andrey G, Preobrajenski Alexei B, Vinogradov Alexander S
V.A. Fock Institute of Physics, St. Petersburg State University, 198504 St. Petersburg, Russia.
Institute of Chemistry, St. Petersburg State University, 198504 St. Petersburg, Russia.
Phys Chem Chem Phys. 2021 May 12;23(18):11015-11027. doi: 10.1039/d1cp00511a.
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 2pπ orbitals of carbon atoms in phenyl groups of the salen macrocycle. The unoccupied MOs above the LUMO reflect σ- and π-bonding between Ni and its nearest neighbours. All valence states have highly mixed character. The specific nature of the unoccupied Ni 3d-derived σ-MO is a consequence of donor-acceptor chemical bonding in [Ni(Salen)].
通过X射线光电子能谱和吸收光谱结合密度泛函理论（DFT）计算，研究了[Ni(Salen)]分子配合物（NiO₂N₂C₁₆H₁₄）占据和未占据价电子态（分子轨道，MOs）的性质和结构。结果，确定了高能占据态和低能未占据电子态的组成。特别地，发现该配合物的最高占据分子轨道（HOMO）主要位于salen配体的苯环上，而与占据的Ni 3d衍生分子轨道（MOs）相关的态具有更高的结合能。最低未占据分子轨道（LUMO）也位于salen配体上，由salen大环苯环中碳原子的2pπ轨道形成。LUMO以上的未占据MOs反映了Ni与其最近邻之间的σ键和π键。所有价态都具有高度混合的特征。未占据的Ni 3d衍生σ-MO的特殊性质是[Ni(Salen)]中供体-受体化学键的结果。
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