Solvothermal One-Pot Synthesis of a New Family of Chiral [Fe4O4]-Cubane Clusters with Redox Active Cores

The two achiral ligands tris(1-methyl-1H-imidazol-2-yl)methanol ((mim)3COH) and bis(1-methyl-1H-imidazol-2-yl)(3-methylpyridin-2-yl)methanol ((mim)2(mpy)COH) form on reaction with Fe(BF4)2∙6H2O, the octahedral low-spin complexes [Fe((mim)3COH)2](BF4)2∙MeCN (1) [Fe((mim)2(mpy)COH)2](BF4)2∙0.5MeCN (2). Both immediately rearrange to chiral [Fe4O4]-cubane clusters [Fe4(mim)3CO)4](BF4)4 (3) [Fe4(mim)3CO)4](BF4)4∙CHCl3 (4), whereas highly symmetrical 3 crystallizes as racemate, 4 resolves based asymmetry introduced by 2-methylpyridine moiety an enantiomerically pure sample. feature redox active cores up four individual accessible states, which directs towards a potential application electron-shuttle.