Mesogenic butadiene-tricarbonyliron complexes6and 7 have been obtained in optically active forms and they exhibit columnar, cholesteric, smectic A and smectic C properties. Both smectic mesophases can potentially be used in switchable bistable electro-optic devices and all the mesogenic enantiomers can act as dopants by inducing ferroelectric properties when dissolved in a non-chiral smectic A or C phase.