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Mn₁₂ -Acetate Complexes Studied as Single Molecules.

ABSTRACT: The phenomenon of single molecule magnet (SMM) behavior of mixed valent Mn₁₂ coordination clusters of general formula [Mn^III ₈ Mn^IV ₄ O₁₂ (RCOO)₁₆ (H₂ O)₄ ] had been exemplified by bulk samples of the archetypal [Mn^III ₈ Mn^IV ₄ O₁₂ (CH₃ COO)₁₆ (H₂ O)₄ ] (4) molecule, and the molecular origin of the observed magnetic behavior has found support from extensive studies on the Mn₁₂ system within crystalline material or on molecules attached to a variety of surfaces. Here we report the magnetic signature of the isolated cationic species [Mn₁₂ O₁₂ (CH₃ COO)₁₅ (CH₃ CN)]⁺ (1) by gas phase X-ray Magnetic Circular Dichroism (XMCD) spectroscopy, and we find it closely resembling that of the corresponding bulk samples. Furthermore, we report broken symmetry DFT calculations of spin densities and single ion tensors of the isolated, optimized complexes [Mn₁₂ O₁₂ (CH₃ COO)₁₅ (CH₃ CN)]⁺ (1), [Mn₁₂ O₁₂ (CH₃ COO)₁₆ ] (2), [Mn₁₂ O₁₂ (CH₃ COO)₁₆ (H₂ O)₄ ] (3), and the complex in bulk geometry [Mn^III ₈ Mn^IV ₄ O₁₂ (CH₃ COO)₁₆ (H₂ O)₄ ] (5). The found magnetic fingerprints - experiment and theory alike - are of a remarkable robustness: The Mn^IV ₄ core bears almost no magnetic anisotropy while the surrounding Mn^III ₈ ring is highly anisotropic. These signatures are truly intrinsic properties of the Mn₁₂ core scaffold within all of these complexes and largely void of the environment. This likely holds irrespective of bulk packing effects.

SUBMITTER: Tombers M

PROVIDER: S-EPMC9299852 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:Similar synthetic schemes yield two different metallacrown (MC) complexes: bis-(μ-3-chloro-benzoato)hexa-kis-(di-methyl-formamide)-tetra-kis-(μ4-N,2-dioxido-benzene-1-carboximidato)tetra-manganese(III)disodium(I), [Mn4Na2(C7H4ClO2)2(C7H4NO3)4(C3H7NO)6] or Na2(3-chloro-benzoate)2[12-MCMn(III)N(shi)-4](DMF)6, 1, and tetra-μ-aqua-tris-(μ-3-chloro-benzoato)(di-methyl-formamide)-tetra-kis-(μ4-N,2-dioxido-benzene-1-carboximidato)penta-manganese(III)sodi-um(I) di-methyl-formamide tetra-solvate 0.72-hydrate, [Mn5Na(C7H4ClO2)3(C7H4NO3)4(C3H7NO)(H2O)4]·4C3H7NO·0.718H2O or MnNa(3-chloro-benzo-ate)3[12-MCMn(III)N(shi)-4](DMF)(H2O)4·4DMF·0.72H2O, 2, where shi3- is salicyl-hydrox-imate and DMF is N,N-di-methyl-formamide. Both complexes have the same framework consisting of four MnIII ions in the MC ring and four shi3- ligands, resulting in an overall square-shaped mol-ecule. The MnIII ions are either five- or six-coordinate with elongated bond lengths in the apical or axial direction, respectively. The structure of 1 is nearly planar, and the MC binds two Na+ ions on opposite faces of the MC central cavity. The 3-chloro-benzoate anions also bind on opposite faces of the MC and form bridges between the central Na+ ions and the ring MnIII ions. For 1 the metallacrown mol-ecule, except for the central Na+ ion, exhibits whole mol-ecule disorder over two sets of sites. Both moieties are centrosymmetric and are related to each other by a pseudo-mirror operation with opposite sense of rotation around the Na⋯Na axis. The occupancy ratio of the main disorder of the metallacrown mol-ecules and 3-chloro-benzoate anions refined to 0.9276 (9):0.0724 (9). The structure of 2 is slightly domed, and the MC binds both an MnII ion and an Na+ ion in the MC central cavity. The MnII ion is located on the convex side of the MC, while the Na+ ion binds to the concave side. Complex 2 represents the first instance of a [12-MCMn(III)N(shi)-4] mol-ecule binding both 3d transition metal and alkali metal ions in the central cavity. In addition, three 3-chloro-benzoate anions bind on the convex side of the MC and connect the MnII ion to three of the ring MnIII ions.

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