Thermotropic nematic order upon nanocapillary filling

Optical birefringence and light absorption measurements reveal four regimes for the thermotropic behavior of a nematogen liquid (7CB) upon sequential filling of parallel-aligned capillaries of 12 nm diameter in a monolithic, mesoporous silica membrane. No molecular reorientation is observed for the first adsorbed monolayer. In the film-condensed state (up to 1 nm thickness), a weak, continuous paranematic-to-nematic (P-N) transition is found, which is shifted by 10 K below the discontinuous bulk transition at T(IN)=305 K. The capillary-condensed state exhibits a more pronounced, albeit still continuous P-N reordering, located 4 K below T(IN). This shift vanishes abruptly upon complete filling of the capillaries. It could originate in competing anchoring conditions at the free inner surfaces and at the pore walls or result from the 10-MPa tensile pressure release associated with the disappearance of concave menisci in the confined liquid upon complete filling. The study documents that the thermo-optical properties of nanoporous systems (or single nanocapillaries) can be tailored over a surprisingly wide range simply by variation of the filling fraction with liquid crystals.