On Packing in Smectics: X-Ray Diffraction Study on the Homologous Series 4, 4′-di-n-alkyl-azoxybenzenes

Abstract

The smectic layer spacings of the homologous series 4,4′-di-n-aLkyl-azoxybenzenes with alkyl chain length from m=6 to m=10 were determined and a mean layer spacing increment of 0.109 nm per methylen group was found.

The results are discussed in relation to two different models:

(I) The diffuse cone model of A. de Vries. Differences between layer spacing and molecular length are attributed to orientational disorder leading to mean tilt angles up to 18° of the molecules.

(II) The second model differentiates between the directions of the rigid aromatic core and that of the alkyl chains. Orthogonality of the rigid core long axis to the smectic layer planes and therefore tilting of the alkyl chains results in coincidence between calculated layer thickness and measured smectic layer spacings.

X-ray film erposures of oriented samples clearly demonstrate the S_A -type of the phases and confirm a slight odd-even effect of layer spacing increments.