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Phosphine Oxide Coordinated Mononuclear LnIII(Ln = DyIII, ErIII) Single-Ion Magnet with Pseudo-Pentagonal Bipyramidal
Soumalya Roy1, Botan Li2, Ezhava Manu Manohar3
1Department of Chemistry, Chonnam National University, 77 Yongbong-ro, Buk-gu, Gwangju, 61186, Korea.
Abstract:
Two mononuclear lanthanide complexes, [(L)LnIII(Ph3PO)Cl]·CH3OH] [LnIII = Dy (1) and Er(2)], are isolated employing a pyridine-based ligand, [2,2'-{(1E, 1'E)-pyridine 2,6-diylbis(methaneylylidine}bis(azaneylylidine)diphenol] (H2L) and triphenylphosphine oxide. Both complexes are characterized by single-crystal X-ray diffraction studies. Pseudo-pentagonal bipyramidal geometry (pseudo-D5h) around the lanthanide centers in both complexes is confirmed through SHAPE analysis. Dynamic magnetic measurements revealed the single-ion magnet behavior for both complexes. However, the energy barrier (Ueff) and relaxation time (τ0) for complex 1are extracted as Ueff = 34.77 K, τ0 = 8.07 × 10-7 s (considering both Orbach and Raman processes). These observed phenomena have been corroborated with the aid of CASSCF-based ab initio calculations.
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