Self-assembly of a novel mixed-valence tetranuclear molecular square [Fe II 3 Fe III L 2 (HL) 2 ] 3+ and [M(HL)] 4 4+ squares (M = Ni, Zn and Cd) {H 2 L = bis(2-acetylpyridine) thiocarbazone}

A novel mixed-valence rigid molecular square [FeII3FeIIIL2(HL)2]3+ was constructed via self-assembly using bis(2-acetylpyridine) thiocarbazone (H2L) as both linker and reducing agent. Single crystal structure analysis shows that each cation is located at an inversion center with four iron atoms at the corners of a square with edge length Fe⋯Fe ca. 4.2 Å. Magnetic measurement exhibits that there is only one FeIII center in each of the tetranuclear squares. There is no significant difference of the coordinated bonds among the four iron centers, indicating that it is impossible to recognize the FeIII in the four iron centers of a square. Electrochemical measurement and UV–VIS–NIR spectral studies demonstrate the Robin–Day class II behavior of the mixed-valence compound with appreciable iron–iron interaction. New rigid metallocyclic squares [Ni(HL)]44+, [Zn(HL)]44+ and [Cd(HL)]44+ were also assembled and structurally characterized for comparison. ESI-MS spectra reveal that the fragments of tetranuclear molecular squares are stable even in solution.