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.

The work introduces the supramolecular assembly of triblock copolymers, namely (PEO)₁₃(PPO)₃₀(PEO)₁₃ (L64), (PPO)₁₄(PEO)₂₄(PPO)₁₄ (17R4), (PPO)₈(PEO)₂₂(PPO)₈ (10R5) and (PEO)₂₁(PPO)₆₇(PEO)₂₁ (P123) with novel cluster complexes [K(diglyme)(CH₃CN)]₂[Mo₆I₁₄] (1) and [K₂(diglyme)(CH₃CN)₅][Mo₆I₁₄] (2) as a route to increase their water solubility. Dynamic light scattering and photophysical measurements reveal the decisive influence of the arrangement of PEO and PPO blocks and of their length on both colloidal and photophysical properties of these solutions. ES-MS data reveal [Mo₆I₁₄]²⁻ clusters as the predominant form in aqueous solutions of L64 and P123. The steady state and time resolved luminescence data indicate concentration dependent sensitizing of the Mo-centered luminescence through the energy transfer from difloxacin to [Mo₆I₁₄]²⁻ mediated by the ion-pairing. The impact of both arrangement and length of PEO and PPO blocks in the luminescent response of [Mo₆I₁₄]²⁻ to difloxacin is discussed. The aqueous solutions of L64 at pH 4 provide the optimal conditions for the sensing of difloxacin through the cluster luminescence.

New tetranuclear heteroleptic complexes [Er₄(dbm)₆(O-btd)₄(OH)₂] (1) and [Er₄(dbm)₄(O-btd)₆(OH)₂] (2) (O-btd = 4-hydroxo-2,1,3-benzothiadiazolate and dbm = dibenzoylmethanide) and their solvates with toluene, THF and CH₂Cl₂ were prepared using two synthetic approaches. The structures of the products were confirmed by single-crystal X-ray diffraction. Magnetic properties of 1 and 2 are in good agreement with X-ray data. The effective magnetic moment (μ_eff) values at 300 K for 1 and 2 corresponds to a system of 4 non-interacting Er(III) ions in the ground state ⁴J_15/2 with g = 6/5. At ambient temperature and upon excitation with λ_exc = 450 nm, complexes 1 and 2 exhibit luminescence at ∼1530 nm, i.e. in the near infra-red (NIR) region. The luminescence intensity grows with increasing the number of the (O-btd)⁻ ligands in the complexes. This observation suggests (O-btd)⁻ as a new efficient antenna ligand for the lanthanide-based NIR luminescence.

For the first time amphiphilic receptors based on the 1,3-alternate stereoisomeric form of thiacalix[4]arene, bearing carboxyl/sulphonate polar headgroups on one side and 10,12-pentacosadiynoic acid (PCDA) residues on another side of the macrocyclic plane, were synthesized. It was shown that embedding of synthesized macrocycles in PCDA vesicles results in stable colloids with a size around 300 nm. The temperature of ultrasonication before UV irradiation has a critical impact on the packing of vesicles for better polymerization. The increase of calixarene content in PCDA vesicles causes a decrease in the degree of PCDA polymerization. Nevertheless, calixarene additives dramatically change the colorimetric response of photopolymerized PCDA vesicles toward metal ions. Vesicles with 10 mol% content of calixarene have significant colorimetric response toward lanthanide ions with a detection limit up to 8 μM. The colorimetric response in the series of lanthanide ions depends on the ionic radius, and the greatest response was found for the largest La(III) ion. It was found that binding of calixarene–PCDA vesicles with lanthanide ions results in the formation of large 1 μm aggregates followed by sedimentation. Thus, the mechanism of colorimetric response of calixarene-decorated polydiacetylene vesicles toward lanthanide ions includes the distortion of the calixarene cavity provoking perturbation of the PDA backbone accompanied by metal-induced aggregation of functionalized vesicles with sedimentation of particles. Therefore, calixarene–PCDA vesicles have great potential for the future design of bifunctional colloids with sensor and separation applications.