Ferrocene and ruthenocene have been incorporated into a range of conjugated
systems. The interaction of these metallocene donor moieties with conjugat
ed substituents is more complex than that of organic donors; both metal-bas
ed and ligand-based orbitals of the metallocene interact with the orbitals
of the pi-system. Here we review the role of these interactions in giving r
ise to a variety of interesting properties including non-linear optical act
ivity in donor-acceptor systems, mixed-valence behaviour in bis(ferrocenyl)
compounds, and structural distortions in polymethines.