Tetranuclear Manganese Complexes with [MnII4] and [MnII2MnIII2] Units: Syntheses, Structures, Magnetic Properties, and DFT Study

Lucjan B. Jerzykiewicz, Józef Utko, Marek Duczmal, Przemysław Starynowicz, Piotr Sobota

doi:10.1002/ejic.201000381

<jats:title>Abstract</jats:title><jats:p>Two tetranuclear manganese compounds, [Mn<jats:sub>4</jats:sub>(μ<jats:sub>3</jats:sub>,η<jats:sup>2</jats:sup>‐L)<jats:sub>4</jats:sub>Br<jats:sub>4</jats:sub>(LH)<jats:sub>4</jats:sub>] (<jats:bold>1</jats:bold>) and [Mn<jats:sub>4</jats:sub>(μ<jats:sub>3</jats:sub>,η<jats:sup>2</jats:sup>‐L)<jats:sub>2</jats:sub>(μ,η<jats:sup>2</jats:sup>‐L)<jats:sub>4</jats:sub>L<jats:sub>2</jats:sub>Br<jats:sub>2</jats:sub>] (<jats:bold>2</jats:bold>), with cubane and defect dicubane‐like cores were synthesized and characterized by single‐crystal X‐ray diffraction, magnetic measurements, and DFT calculations (LH = 2‐methoxyethanol). The magnetic properties of the resulting [Mn<jats:sub>4</jats:sub>] building blocks are presented and discussed in detail. In particular, in <jats:bold>2</jats:bold> the Mn<jats:sup>III</jats:sup>–O–Mn<jats:sup>III</jats:sup> angle 103.12(8)° is the largest observed to date for such a system. The conjunction of antiferromagnetic and ferromagnetic interactions within the tetranuclear mixed‐valent Mn<jats:sup>II</jats:sup><jats:sub>2</jats:sub>Mn<jats:sup>III</jats:sup><jats:sub>2</jats:sub> complexes results in an unusual <jats:italic>S</jats:italic><jats:sub>T</jats:sub> = 1 ground state.</jats:p>

Tetranuclear Manganese Complexes with [Mn<sup>II</sup><sub>4</sub>] and [Mn<sup>II</sup><sub>2</sub>Mn<sup>III</sup><sub>2</sub>] Units: Syntheses, Structures, Magnetic Properties, and DFT Study

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