M. Hobi et al., PARAMAGNETIC AND SEMICONDUCTING 1 1 SALTS OF 1,1'-DISUBSTITUTED FERROCENES AND [NI(MNT)(2)](-) - SYNTHESIS, STRUCTURE, AND PHYSICAL-PROPERTIES/, Organometallics, 15(25), 1996, pp. 5342-5346
The ferrocene-based electron donors bis[2-(4-(methylthio)phenyl)-(E)-e
thenyl]ferrocene (2), 1,1'-bis[2-(4-methoxyphenyl)-(E)-ethenyl]ferroce
ne (3), iolo[4,5-b][1,3]dithiol-2-ylidene)methyl]ferrocene (4), and '-
bis[(1,3-benzodithiol-2-ylidene)methyl]ferrocene (5) were found to rea
ct with ferrocenium bis(maleonitriledithiolato)nickelate (1-) ([FeCp(2
)](+)[Ni(mnt)(2)](-), 6) to afford the corresponding 1:1 paramagnetic
salts 7-10, containing 1,1'-disubstituted ferrocenium derivatives. SQU
ID magnetic susceptibility measurements of these new compounds showed
a behavior dominated by antiferromagnetic interactions within pairs of
[Ni(mnt)(2)](-) ions. Pressed pellets of compounds 7 ([2][Ni(mnt)(2)]
) and 9 ([4][Ni(mnt)(2)]) are semiconducting, with a relatively large
conductivity activation energy (0.85 and 1.13 eV). Crystals of 7 revea
l the monodimensional nature of the compound. Each separate stack of [
Ni(mnt)(2)](-) ions is flanked by two ferrocenium stacks. Ni-Ni distan
ces alternate between 3.67 and 3.99 Angstrom.