Investigating magnetostructural correlations in the pseudooctahedral trans-[Ni(II){(OPPh2)(EPPh2)N}2(sol)2] complexes (E = S, Se; sol = DMF, THF) by magnetometry, HFEPR, and ab initio quantum chemistry.
In this work, magnetometry and high-frequency and -field electron paramagnetic resonance spectroscopy (HFEPR) have been employed in order to determine the spin Hamiltonian (SH) parameters of the non-Kramers, S = 1, pseudooctahedral trans-[Ni(II){(OPPh(2))(EPPh(2))N}(2)(sol)(2)] (E = S, Se; sol = DMF, THF) complexes. X-ray crystallographic studies on these compounds revealed a highly anisotropic NiO(4)E(2) coordination environment, as well as subtle structural differences, owing to the nature of the Ni(II)-coordinated solvent molecule or ligand E atoms. The effects of these structural characteristics on the magnetic properties of the complexes were investigated. The accurately HFEPR-determined SH zero-field-splitting (zfs) D and E parameters, along with the structural data, provided the basis for a systematic density functional theory (DFT) and multiconfigurational ab initio computational analysis, aimed at further elucidating the electronic structure of the complexes. DFT methods yielded only qualitatively useful data. However, already entry level ab initio methods yielded good results for the investigated magnetic properties, provided that the property calculations are taken beyond a second-order treatment of the spin-orbit coupling (SOC) interaction. This was achieved by quasi-degenerate perturbation theory, in conjunction with state-averaged complete active space self-consistent-field calculations. The accuracy in the calculated D parameters improves upon recovering dynamic correlation with multiconfigurational ab initio methods, such as the second-order N-electron valence perturbation theory NEVPT2, the difference dedicated configuration interaction, and the spectroscopy-oriented configuration interaction. The calculations showed that the magnitude of D (∼3-7 cm(-1)) in these complexes is mainly dominated by multiple SOC contributions, the origin of which was analyzed in detail. In addition, the observed largely rhombic regime (E/D = 0.16-0.33) is attributed to the highly distorted metal coordination sphere. Of special importance is the insight by this work on the zfs effects of Se coordination to Ni(II). Overall, a combined experimental and theoretical methodology is provided, as a means to probe the electronic structure of octahedral Ni(II) complexes.
Inorganic Chemistry Laboratory, Department of Chemistry, National and Kapodistrian University of Athens, 15771 Athens, Greece.
Dimitrios
D
Maganas
J
J
Krzystek
Eleftherios
E
Ferentinos
Alexander M
AM
Whyte
Neil
N
Robertson
Vassilis
V
Psycharis
Aris
A
Terzis
Frank
F
Neese
Panayotis
P
Kyritsis
D056831:Coordination Complexes / Q000138:chemical synthesis / Q000737:chemistry*; D018360:Crystallography, X-Ray; D004578:Electron Spin Resonance Spectroscopy; D008280:Magnetics; D060306:Magnetometry; D008958:Models, Molecular; D015394:Molecular Structure; D009532:Nickel / Q000737:chemistry*; D011789:Quantum Theory; D013237:Stereoisomerism
D056831:Coordination Complexes; D009532:Nickel