Magnetic Properties and Electronic Structure of the S = 2 Complex [MnIII{(OPPh2)2N}3] Showing Field-Induced Slow Magnetization Relaxation

Yiannis Sanakis; J Krzystek; Dimitrios Maganas; Alexios Grigoropoulos; Eleftherios Ferentinos; Marios G Kostakis; Vasiliki Petroulea; Michael Pissas; Komalavalli Thirunavukkuarasu; Wolfgang Wernsdorfer; Frank Neese; Panayotis Kyritsis

doi:10.1021/acs.inorgchem.0c01636

Magnetic Properties and Electronic Structure of the S = 2 Complex [Mn^III{(OPPh₂)₂N}₃] Showing Field-Induced Slow Magnetization Relaxation

Inorg Chem. 2020 Sep 21;59(18):13281-13294. doi: 10.1021/acs.inorgchem.0c01636. Epub 2020 Sep 8.

Affiliations

¹ Institute of Nanoscience and Nanotechnolgy, National Centre of Scientific Research "Demokritos", Aghia Paraskevi 15310, Attiki, Greece.
² National High Magnetic Field Laboratory, Florida State University, Tallahassee, Florida 32310, United States.
³ Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Mülheim an der Ruhr, Germany.
⁴ Inorganic Chemistry Laboratory, Department of Chemistry, National and Kapodistrian University of Athens, 15771 Athens, Greece.
⁵ Analytical Chemistry Laboratory, Department of Chemistry, National and Kapodistrian University of Athens,15771 Athens, Greece.
⁶ Department of Physics, Florida A&M University, 111 Jones Hall, Tallahassee, Florida 32307, United States.
⁷ Physikalisches Institut, Karlsruher Institut für Technologie, Wolfgang-Gaede-Strasse 1, 76131 Karlsruhe, Germany.
⁸ Institute of Quantum Materials and Technologies, Karlsruher Institut für Technologie, Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany.

PMID: 32897702
DOI: 10.1021/acs.inorgchem.0c01636

Abstract

The high-spin S = 2 Mn(III) complex [Mn{(OPPh₂)₂N}₃] (1_Mn) exhibits field-induced slow relaxation of magnetization (Inorg. Chem. 2013, 52, 12869). Magnetic susceptibility and dual-mode X-band electron paramagnetic resonance (EPR) studies revealed a negative value of the zero-field-splitting (zfs) parameter D. In order to explore the magnetic and electronic properties of 1_Mn in detail, a combination of experimental and computational studies is presented herein. Alternating-current magnetometry on magnetically diluted samples (1_Mn/1_Ga) of 1_Mn in the diamagnetic gallium analogue, [Ga{(OPPh₂)₂N}₃], indicates that the slow relaxation behavior of 1_Mn is due to the intrinsic properties of the individual molecules of 1_Mn. Investigation of the single-crystal magnetization of both 1_Mn and 1_Mn/1_Ga by a micro-SQUID device reveals hysteresis loops below 1 K. Closed hysteresis loops at a zero direct-current magnetic field are observed and attributed to fast quantum tunneling of magnetization. High-frequency and -field EPR (HFEPR) spectroscopic studies reveal that, apart from the second-order zfs terms (D and E), fourth-order terms (B₄^m) are required in order to appropriately describe the magnetic properties of 1_Mn. These studies provide accurate spin-Hamiltonian (sH) parameters of 1_Mn, i.e., zfs parameters |D| = 3.917(5) cm^-1, |E| = 0.018(4) cm^-1, B⁰₄ = B₄² = 0, and B₄⁴ = (3.6 ± 1.7) × 10^-3 cm^-1 and g = [1.994(5), 1.996(4), 1.985(4)], and confirm the negative sign of D. Parallel-mode X-band EPR studies on 1_Mn/1_Ga and CH₂Cl₂ solutions of 1_Mn probe the electronic-nuclear hyperfine interactions in the solid state and solution. The electronic structure of 1_Mn is investigated by quantum-chemical calculations by employing recently developed computational protocols that are grounded on ab initio wave function theory. From computational analysis, the contributions of spin-spin and spin-orbit coupling to the magnitude of D are obtained. The calculations provide also computed values of the fourth-order zfs terms B₄^m, as well as those of the g and hyperfine interaction tensor components. In all cases, a very good agreement between the computed and experimentally determined sH parameters is observed. The magnetization relaxation properties of 1_Mn are rationalized on the basis of the composition of the ground-state wave functions in the absence or presence of an external magnetic field.