Porous molecular crystals of calix[4]arenes

X-ray diffraction, thermogravimetric, and adsorption measurements were applied to study the thermal decomposition of the complexes of 25,26,27,28-tetrahydroxycalix4]arene and 4-tert-butylcalix4]arene with the solvents resulting in the formation of porous phases. Diffusion of the "guest" (solvent, gas) through the molecular crystal of calixarene-host proceeds via the consecutive formation of a series of thermodynamically unstable porous phases of the "host." Owing to the structural reorganization of calixarene, the transport of the "guest" occurs through the "host" matrix followed by complexation and formation of the thermodynamically stable structure.