Large negative thermal-expansion coefficients of a partially perfluori
nated liquid-crystal compound as a function of temperature and number
of layers have been obtained from free-standing films. Exploiting this
behavior, as well as novel layer-by-layer thinning transitions, we ha
ve demonstrated the existence of an anomalous layer compression. For a
3-layer film, the magnitude of total compression was found to be as l
arge as 3 Angstrom.