Synthesis, Magnetic Properties, and X-ray Spectroscopy of Divalent Cobalt(II) and Nickel(II) Cubanes [M4II(HL2)4(OAc)4]

Scheurer A, Korzekwa J, Nakajima T, Hampel F, Buling A, Derks C, Neumann M, Joly L, Petukhov K, Gieb K, Müller P, Kuepper K, Meyer K (2015)

Publication Language: English

Publication Type: Journal article, Report

Publication year: 2015

Journal

Publisher: Wiley-VCH Verlag

Pages Range: 1872–1901

Journal Issue: 11

URI: http://onlinelibrary.wiley.com/doi/10.1002/ejic.201402988/abstract

DOI: 10.1002/ejic.201402988

Abstract

Under anaerobic conditions, the reactions of cobalt(II) and nickel(II) acetate tetrahydrate with 2,6-pyridinedimethanol (H₂L², 3) in anhydrous acetonitrile afforded two tetranuclear metal(II) complexes [M^II₄(HL²)₄(OAc)₄] (4; M^II = Co²⁺, Ni²⁺) with a [M₄(μ₃-O)₄]⁴⁺ cubane core. X-ray structural analyses revealed that both M^II cubanes 4a·2CH₃OH and 4b·2CH₃OH are isostructural and crystallize in the tetragonal space group I4₁/acd with eight molecules in the unit cell. In the solid state, the orientation of the cubane cores of 4 and the formation of a 3D framework were controlled by π–π interactions as well as intra- and intermolecular O–H···O hydrogen bonds. Variable-temperature magnetic susceptibility measurements revealed that the cubanes 4 show a ferrimagnetic coupling scheme that leads to a diamagnetic ground state for both complexes. Core-level X-ray photoelectron spectroscopy confirmed that the Co and Ni ions in 4a and 4b are in a divalent state. X-ray magnetic circular dichroism was performed to extract the spin and orbital contributions to the Co and Ni magnetic moments. We compared the experimental results of the local electronic structures around the Co²⁺ ions in 4a and the Ni²⁺ ions in 4b with charge-transfer multiplet simulations.

Authors with CRIS profile

Involved external institutions

Universität Osnabrück Germany (DE) Université de Strasbourg (UDS) France (FR) Nara Women's University / 奈良女子大学 Japan (JP)

How to cite

APA:

Scheurer, A., Korzekwa, J., Nakajima, T., Hampel, F., Buling, A., Derks, C.,... Meyer, K. (2015). Synthesis, Magnetic Properties, and X-ray Spectroscopy of Divalent Cobalt(II) and Nickel(II) Cubanes [M4II(HL2)4(OAc)4]. European Journal of Inorganic Chemistry, 11, 1872–1901. https://doi.org/10.1002/ejic.201402988

MLA:

Scheurer, Andreas, et al. "Synthesis, Magnetic Properties, and X-ray Spectroscopy of Divalent Cobalt(II) and Nickel(II) Cubanes [M4II(HL2)4(OAc)4]." European Journal of Inorganic Chemistry 11 (2015): 1872–1901.

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