TY - JOUR
T1 - A MnII6MnIII6 single-strand molecular wheel with a reuleaux triangular topology
T2 - Synthesis, structure, magnetism, and DFT studies
AU - Zartilas, Sotiris
AU - Papatriantafyllopoulou, Constantina
AU - Stamatatos, Theocharis C.
AU - Nastopoulos, Vassilios
AU - Cremades, Eduard
AU - Ruiz, Eliseo
AU - Christou, George
AU - Lampropoulos, Christos
AU - Tasiopoulos, Anastasios J.
PY - 2013/10/21
Y1 - 2013/10/21
N2 - 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.
AB - 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.
UR - https://www.scopus.com/pages/publications/84886669333
U2 - 10.1021/ic401872c
DO - 10.1021/ic401872c
M3 - Article
SN - 0020-1669
VL - 52
SP - 12070
EP - 12079
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 20
ER -