A new azobenzene-containing gelator for low-molar-mass liquid crystals (LCs
) was synthesized. It can effectively gel nematic LCs such as E7 through th
e formation of a hydrogen-bonded network. Moreover, an intriguing self-asse
mbly process was observed. When thin films of the E7/gelator mixture, cast
on CaF2 crystal windows or glass slides, are cooled from the isotropic phas
e, at temperatures below but close to the sol-gel phase transition, aggrega
tion of the gelator starts from the edge of the film, and the fiberlike agg
regates grow predominantly normal to the edge, leading to the formation of
an oriented network at the macroscopic scale in the liquid gel state. On fu
rther cooling through the phase transition from liquid gel to nematic gel,
the aligned fiberlike aggregates induce a long-range molecular orientation
of E7, in the direction perpendicular to the fibers. The end result of this
is a self-assembled anisotropic LC gel formed in the absence of any extern
al effects such as surface treatment for the substrates or irradiation for
the azobenzene groups on the gelator molecules.