A MnII6MnIII6 single-strand molecular wheel with a reuleaux triangular topology: Synthesis, structure, magnetism, and DFT studies
Date
2013Author
Zartilas, Sotiris M.![ORCID logo](https://orcid.org/sites/default/files/images/orcid_16x16.png)
![ORCID logo](https://orcid.org/sites/default/files/images/orcid_16x16.png)
![ORCID logo](https://orcid.org/sites/default/files/images/orcid_16x16.png)
Cremades, E.
Ruiz, E.
Christou, George
![ORCID logo](https://orcid.org/sites/default/files/images/orcid_16x16.png)
![ORCID logo](https://orcid.org/sites/default/files/images/orcid_16x16.png)
Source
Inorganic chemistryVolume
52Issue
20Pages
12070-12079Google Scholar check
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The use of the anion of 3-methyl-1,3,5-pentanetriol (mpt3-) in manganese carboxylate chemistry has afforded the new MnII/III 12 cluster [MnII6MnIII 6(mpt)6(CH3CO2)12(py) 6]·3CH3CN (1·3CH3CN). Complex 1 was isolated in moderate yield by the reaction of Mn(CH3CO 2)2·4H2O and H3mpt in a 2.6:1 molar ratio in a solvent mixture of acetonitrile and pyridine. The structure of 1 consists of alternating [MnII2(CH3CO 2)3(py)]+ and [MnIII 2(μ-OR)2(CH3CO2)(py)] 3+ dimeric units (three of each dimer), linked at each end by two alkoxo and one acetate bridges the mpt3- ligands adopt the η2:η2:η2:μ4 coordination mode. The overall metal topology of this new Mn12 wheel resembles a guitar plectrum, or a Reuleaux triangle. Complex 1 displays an unprecedented structural topology, being the first example of a Mn II6MnIII6 wheel constructed from alternating homovalent dimers and the only known Mn12 loop with the trigonal symmetry of a Reuleaux triangle (all other reported loops were ellipsoids). Variable-temperature, solid-state direct- and alternating-current magnetization studies were carried out on complex 1, revealing the presence of antiferromagnetic exchange interactions between the metal ions in the molecule, which lead to a spin ground-state value S = 0 the exchange coupling parameters J were calculated using density functional theory employing a hybrid B3LYP functional. © 2013 American Chemical Society.