The interest in functional supramolecular systems for the design of innovative materials and technologies, able to fundamentally change the world, is growing at a high pace. The huge array of publications that appeared in recent years in the global literature calls for systematization of the structural trends inherent in the formation of these systems revealed at different molecular platforms and practically useful properties they exhibit. The attention is concentrated on the topics related to functional supramolecular systems that are actively explored in institutes and universities of Russia in the last 10–15 years, such as the chemistry of host–guest complexes, crystal engineering, self-assembly and self-organization in solutions and at interfaces, biomimetics and molecular machines and devices.The bibliography includes 1714 references.

Molecular recognition of vaporous guests by the solid hosts 2,2′-bis(9-hydroxyfluoren-9-yl)biphenyl (1) and tert-butylcalix[4]arene (2) was studied. For this purpose the vapour sorption isotherms of 15 organic compounds with various molecular size and group composition with the solid hosts 1 and 2 were determined by static gas chromatographic headspace analysis. Most of the isotherms obtained show a definite inclusion threshold at a specific guest activity and a saturation part corresponding to the formation of stoichiometric supramolecular compounds. The stoichiometry of the host–guest compounds and free energies of their formation based on different standard states were determined. The free energy of guest transfer from the standard state of an infinitely dilute guest solution in toluene to the solid inclusion compound was assumed to be a molecular recognition parameter in the systems studied. For host 1 this transfer free energy exhibits a reasonably good 2-parameter correlation with guest molar refraction and free energy of H-bonding between guest and alcohols. Bad correlation was obtained for solid host 2. The effect of the guest structural parameters on molecular recognition by hosts 1 and 2 is discussed in terms of the different size of potential cavities in the host crystals and different ability of the hosts to H-bond with guests.