Numerous heteroleptic 2,6-di-tert-butyl-4-methylphenolate (BHT) magnesium complexes have been synthesized by treatment of (BHT)MgBu(THF)₂ with various alcohols. Molecular structures of the complexes have been determined by X-ray diffraction. The magnesium coordination number in [(BHT)Mg(μ-OBn)(THF)]₂ (3) and [(BHT)Mg(μ-O-tert-BuC₆H₄)(THF)]₂ (4) is equal to 4. Complexes formed from esters of glycolic and lactic acids, [(BHT)Mg(μ-OCH₂COOEt)(THF)]₂ (5) and [(BHT)Mg(μ-OCH(CH₃)COOCH₂COO^tBu)(THF)]₂ (6) contain chelate fragments with pentacoordinated magnesium. Compounds 3–6 contain THF molecules coordinated to magnesium atoms. Complex {(BHT)Mg[μ-O(CH₂)₃CON(CH₃)₂]}₂ (7) does not demonstrate any tendency to form an adduct with THF. It has been experimentally determined that complexes 3 and 5 are highly active catalysts of lactide polymerization. The activity of 4 is rather low, and complex 7 demonstrates moderate productivity. According to DOSY NMR experiments, compounds 3 and 5 retain their dimeric structures even in THF. The free energies of model dimeric [(DBP)Mg(μ-OMe)(Sub)]₂ and monomeric (DBP)Mg(OMe)(Sub)₂ products on treatment of [(DBP)Mg(μ-OMe)(THF)]₂ with a series of σ-electron donors (Sub) have been estimated by DFT calculations. These results demonstrate that the substitution of THF by Sub in a dimeric molecule is an energetically allowed process, whereas the dissociation of dimers is energetically unfavorable. DFT modeling of ε-CL and (DL)-lactide ROP catalyzed by dimeric and monomeric complexes showed that a cooperative effect of two magnesium atoms occurs within the ROP for binuclear catalytic species. A comparison of the reaction profiles for ROP catalyzed by binuclear and mononuclear species allowed us to conclude that the binuclear mechanism is favorable in early stages of ROP initiated by dimers 3 and 5.

The synthesis of functionalized porphyrins and their conjugates from meso-tetraarylporphyrins through the acylation and the oxidation of β-aminoporphyrins was investigated. 2,3-Dioxochlorins were prepared by the oxidation of a variety of β-aminoporphyrins and subsequently used in a condensation reaction with functionalized aromatic aldehydes and ammonium acetate to form β-functionalized porphyrins bearing a fused imidazole ring. Under optimized experimental conditions both reactions tolerate various functional groups and afford the products in an appropriate overall yield. The mildness and usefulness of this methodology are illustrated by several examples including the synthesis of porphyrins bearing receptor groups and water-solubilizing moieties.

In this work, a previously undescribed phenomenon of orientation-induced redox isomerism in a Langmuir monolayer is revealed in the case of cerium bis-[tetra-(15-crown-5)-phthalocyaninate]-(Ce[(15C5)₄Pc]₂). It was established that intramolecular electron transfer (IET) from the electronic system of phthalocyanine to the 4f-orbital of cerium atom occurs upon spreading of a (Ce[(15C5)₄Pc]₂) chloroform solution onto the air–water interface (3D → 2D IET). This process is related to the transformation of Ce⁴⁺ cation in the solution to Ce³⁺ in the monolayer. It was also found that reversible Ce³⁺ ↔ Ce⁴⁺ IETs occur upon compression (π₁ → π₂) and expansion (π₂ → π₁) of monolayer (2D^π1 ↔ 2D^π2 IET, π-surface pressure). The mechanism of genuine redox isomerism was confirmed by the results of in situ UV–vis spectral measurements performed on monolayers and Langmuir–Blodgett films, AFM, and XPS studies of Langmuir–Blodgett films transferred at different surface pressures. The understanding of this reversible IET mechanism is especially important due to possible applications of such redox-isomeric systems in the development of nanoscale multibit information storage devices.

The unique properties of porous metal-organic frameworks are responsible for the increasing research interest in the design and synthesis of this type of materials. A general strategy towards targeted design of metal-organic frameworks possessing desired properties is a choice of optimal linkers, which are usually represented by polytopic organic ligands. Porphyrins are promising building blocks for such frameworks due to their tunable physicochemical properties and wide possibilities of macrocycle modification. The achievements of the last decade in the development of synthetic approaches to porphyrin functionalization have promoted fast progress of tetrapyrrole chemistry as the basis of metal-organic frameworks. This review gives analysis of the current literature devoted to the synthesis of porphyrin-based metal-organic frameworks and the prospects for their application in modern materials science. The bibliography includes 262 references.