Project aimed on implementation of crystal engineering approach and X-ray crystallography for design and creation of crystalline hybrid organic/inorganic materials with advanced physical and biologically active functions. Metal–organic materials (MOMs) include multinuclear clusters and metal–organic frameworks (MOFs) with the regular network structures, pore spaces in a crystalline lattice, and a high degree of functionality. It is a class of materials recognized for their flexibility with regard to structural design and can be modified to suit specific applications: molecular spintronic devices, energy (H₂, CH₄) storage, gases separation, as stimuli responsive materials with optical or magnetic responses to the guest inclusion. MOMs have potential for environmentally friendly and economically favorable capture of greenhouse gases, adsorption heat transformation for energy-saving air conditioning, and as drugs carriers that is increasingly important for the future world economy. Multiple component supramolecular compounds (SCs) are also attractive target for design and tuning of properties through the manipulation by weaker than coordination bonds interactions like hydrogen bonds, stacking and halogen•••halogen interactions. Cocrystallization is a technique for modifying and improving the physicochemical and pharmacokinetic properties of bioactive or pharmaceutical ingredients embodying the concept of supramolecular synthon. Cocrystallization of two or more bioactive entities can be employed for delivery of their combination for the better and efficacious biological effect. The rational design of MOMs and SCs is based on crystal engineering principles, which involve the concept of Molecular/Supermolecular Building Blocks, Secondary Building Units, “node and spacer” approach, structural modularity, reticular and scale chemistry, supramolecular synthons. For example, the combinations of organic ligands and metal ions/clusters may result in the topologically similar multifunctional MOMs in which two or more physical/chemical properties are integrated, tuning the properties of advanced organic luminescent materials may be achieved by coordination their molecules to metal atoms which influence on the manner of their aggregation in crystal; cocrystals can improve the physicochemical properties of drugs without compromising their therapeutic benefit.

The objectives of the project were: (i) to develop the protocols for the directed fabrication of perspective MOMs based on homo- and heterometallic coordination compounds of d, f, d-d′, d-f ions, carboxylylic O,N,S-based ligands, Schiff-bases derivatives and SCs with combination of useful properties. Tailoring of material’s properties was realized by appropriate choice of starting components and using different synthetic procedures such as hydro(solvo)thermal and microwave assisted heating, ultrasonic irradiations, and “know-how” methods; (ii) to implement the single crystal X-ray structural study of fabricated materials; (iii) to study the structure–properties relationship using available techniques and national/international collaboration; (iv) to provide a background for training in development of new advanced materials and X-ray crystallography for young researchers, students, and high school students using the existing in the laboratory scientific studio “Eureka”; (v) to prepare proposals for further funding; (vi) to perform research for the application of the project results.