All-round robustness of the Mn19 coordination cluster system: experimental validation of a theoretical prediction

Abstract

Experimental and theoretical studies indicate that achieving the maximum possible ground spin state of S_T = 83/2 for the mixed-valent Mn₁₉ coordination cluster is insensitive to replacement of its eight μ₃-N₃ ligands by μ₃-Cl, μ₃-Br, μ₃-OH or μ₃-OMe, substantiating that the ferromagnetic interactions are indeed mediated mainly by the internal (μ₄-O) ligands. The robustness of the inorganic {Mn^III₁₂Mn^II₇(μ₄-O)₈} core is clear from the molecular structure and ESI-MS studies have shown that the structure of the Mn₁₉ aggregate, and also of its Mn₁₈Y analogue, are stable beyond the solid state.