Langmuir-Blodgett films as aligning layers for homeotropic alignment of liquid crystal molecules

The first single crystal structure of a Group VA halide salt with three equivalent long n-alkyl chains, benzyltrioctadecylammonium bromide (BzN18Br), is reported. It consists of alternating interdigitated and non-interdigitated regions of alkyl chains separated by ionic planes. Two chains per molecule are paired and extend to one side in a non-interdigitated region. The third chain is on the opposite side of the ionic plane and pairs intermolecularly to form an adjacent, interdigitated region. The thickness of two nearly extended molecules defines the bilayer unit-two ionic planes flanked by a region with intramolecularly paired chains and separated by an interdigitated chain region. Powder X-ray diffraction and optical microscopy data of liquid crystalline BzN18Br are consistent with an enantiotropic smectic A₂ (SmA₂) phase: the three n-alkyl chains of each molecule are projected from one side of an ionic plane, and head groups of neighbouring molecules are oriented head-to-head, in a non-interdigitated bilayer assembly. The structure of BzN18Br fills an important gap in our knowledge about the crystal packing of ammonium and phosphonium salts with one-four equivalent long n-alkyl chains. A comparison of their packing arrangements is made and the transitional nature of the BzN18Br structures is demonstrated. Although salts with one, two, or three long n-alkyl chains form SmA₂ phases, each is distinctive in its molecular packing. A large molecular reorganization accompanies the crystal-to-liquid crystal transition of BzN18Br.