Half-integer spin heptanuclear single-molecule magnet with an unusual Mn(III)6Mn(II) exchange-coupled core

• Published in: Inorganic chemistry Vol. 51; no. 8; pp. 4448 - 4457
• Main Authors: Chen, Siou-Yin, Beedle, Christopher C, Gan, Pei-Rung, Lee, Gene-Hsian, Hill, Stephen, Yang, En-Che
• Format: Journal Article
• Language: English
• Published: United States 16.04.2012
• Subjects: Ethanolamines - chemistry; Ligands; Magnets - chemistry; Manganese - chemistry; Models, Molecular; Molecular Conformation; Organometallic Compounds - chemistry; Phenol - chemistry
• ISSN: 1520-510X
• DOI: 10.1021/ic2019154

The synthesis, X-ray crystallography, magnetic properties, and high-field electron paramagnetic resonance (HFEPR) of a new heptanuclear manganese complex [Mn(7)(heamp)(6)](ClO(4))(2)·4CH(2)Cl(2)·H(2)O (complex 2), in which heampH(3) is 2-[N,N-di(2-hydroxyethyl)aminomethyl]phenol (compound 1), is reported. Complex 2 has a hexagonal, disk-shaped topology and contains six Mn(III) ions and a central Mn(II) ion. It crystallizes in the monoclinic space group P2(1)/c with two molecular orientations. Consideration of the cluster topology, together with variable-temperature and variable-field DC magnetic susceptibility data, suggest that complex 2 exists in a half-integer, S = (19)/(2) ± 1 spin ground state, with appreciable uniaxial zero-field splitting (D = -0.16 cm(-1)). AC magnetic susceptibility measurements clearly show out-of-phase signals, which are frequency- and temperature-dependent, indicating slow magnetization relaxation behavior. An analysis of the relaxation data employing the Arrhenius formula yielded an effective relaxation barrier of 12.9 cm(-1). Simulations of HFEPR studies agree with the assignment of an S ≈ (19)/(2) spin ground state, with g = 1.96, D = -4.71 GHz (-0.16 cm(-1)), and a longitudinal fourth-order zero-field splitting parameter B(4)(0) = -2.7 × 10(-4) GHz (-9.0 × 10(-6) cm(-1)).