A series of liq. cryst. vanadyl 5-alkoxy-N,N'-disalicylidenediamine complexes are reported with ethylene (salen), propylene (salpn), and 2,2-dimethylpropylene (Me2salph) groups connecting the Schiff-base nitrogens. These compds. are under investigation as potential ferroelec. and second order nonlinear optical materials. The n(salen)VOs (n = no. of carbons in the alkoxy chain) are monomeric in the solid state and display highly disordered smectic A and smectic C structures as detd. by optical textures and x-ray powder diffraction. In the case of the (n(salpn)VO)s, the compds. exhibit a linear chain structure (e.g. (-V = O -V = O)n) in the solid state. For n(salpn)VO, the linear chain structure is too restrictive to allow a liq. cryst. state and these compds. melt at ∼300° with decompn. The n(Me2salpn)VOs also exhibit a linear chain structure as detd. by an x-ray crystal structure and IR spectroscopy, but steric repulsions weaken the linear chain structure sufficiently to allow melting into the liq. cryst. state. Variable temp. IR shows that the fluid liq. cryst. phase of these compds. exhibits a linear chain structure and becomes monomeric at temps. above their clearing point. X-ray powder diffraction and optical texture anal. show the thermotropic phases of the n(Me2salpn)VO complexes to display smectic structures. These results demonstrate that the n(Me2salpn)VO complexes comprise a new type of low-viscosity liq. cryst. polymer which assembles into a unidirectional linear chain structure. [on SciFinder(R)]