Ferrocene-appended ligands for use in spin crossover-redox "hybrid" complexes of iron(II) and cobalt(II).

In a study of multifunctional ('hybrid') molecular materials, with one function being spin-crossover and the second being reversible redox behaviour, we describe ferrocene-appended ligands and their d(6) and d(7) complexes trans-[Fe(II)(FTP)2(NCS)2] (1), [Co(II)(FTTP)2](ClO4)2·2(MeCN) (2) and [Fe(II)(FTTP)2](ClO4)2·Et2O (3) (where FTP = 4-(2-pyridyl)-1H-1,2,3-triazol-1-ylferrocene and FTTP = 4'-ferrocenyl-2,2':6',2''-terpyridine). The structures, magnetism and solution electrochemistry are described. Complex 1 remains high-spin, 2 displays gradual, incomplete spin crossover and 3 remains low-spin between 350-2 K. The electrochemical results show that one-electron oxidations at the ferrocene group, located external to the coordination site, occur at more positive potentials than the 'inner' M(II/III) couple in 1 and 2, but not in 3, and this has implications for retaining and influencing spin transitions at the M(II) centres, in future.