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Выставка к VII Международной конференции по физической химии краунсоединений, порфиринов и фталоцианинов

Журнальные статьи

1. Alcay Y. et al. New ferrocenyl naphthoquinone fused crown ether chemosensors: Highly selective, kinetically and regio controlled colorimetric, beryllium ion recognition // J. Organomet. Chem. 2018. Vol. 868. P. 131–143.

New organometallic chemosensors which are based on triad molecules, ferrocenyl naphthoquinone linearly/angularly fused crown ethers (Fc-cnq-1a and Fc-cnq-1b) bearing ferrocene, quinone, and crown ether functional groups together, were synthesized and utilized for selective sensing trace amount of Be2+ ion (5.41 mu M) among other metal cations. The UV-vis spectrophotometric titration experiments at controlled temperatures (25-60 degrees C) resulted in characteristic spectral changes in the intramolecular charge-transfer (CT) transitions upon addition of Be2+ ion into the solution of sensors Fc-cnq-1a and Fc-cnq-1b. However, no spectral changes were observed for the other metal cations used for testing at the same conditions, indicating that the sensors can selectively detect Be2+ among the studied metal ions even at higher temperatures. The spectral change in the absorption spectra of the sensors upon addition of Be2+ ion corresponds to the visible region of the spectrum, from deep green to yellow color, and this leads to observe the effect of the Be2+ ion with naked eye. The sensors used for the signaling of Be2+ ion displayed a significant shortening in response time depending on increasing temperature without any degradation of the sensors. Fc-cnq-1a displayed faster response time than Fc-cnq-1b in the temperature range of 35-60 degrees C. The activation energies for the pseudo-first order complexation reactions were calculated as 124.2 +/- 13.0 kJ mol(-1) and 151.9 +/- 18.0 kJ mol(-1) for Fc-cnq-1a and Fc-cnq-1b, respectively, which explains faster response time of Fc-cnq-1a for recognizing Be2+ ion. Density Functional Theory calculations (TD-B97D/TZVP//mPWPW91/6-31 + G(2d,2p) level) were performed on Fc-cnq-1a, Fc-cnq-1b and their Be+2 complexes in order to elucidate their geometries and the molecular orbitals. Calculations have shown comparable results with those obtained from the experimental data. (C) 2018 Elsevier B.V. All rights reserved.


2. Anju K.S. et al. meso-Aryl [20]pi Homoporphyrin: The Simplest Expanded Porphyrin with the Smallest Mobius Topology // Angew. Chem.-Int. Edit. 2017. Vol. 56, № 49. P. 15667–15671.

An unstable conjugated homoporphyrin was successfully stabilized by introducing meso-aryl substitutents. It was evident from the moderate diatropic ring current found by NMR analysis that the newly formed 20 conjugated free base and its protonated form exhibited Mobius aromatic character. Furthermore, complexation as a ligand with an Rh-I ion afforded a unique binding mode and retained the Mobius aromaticity. Overall, these compounds are the smallest Mobius aromatic molecules, as confirmed by spectral and crystal-structure analysis and supported by theoretical studies.


3. Bleve V. et al. Synthesis and Characterisation of a Paramagnetic [2]Rotaxane Based on a Crown Ether-Like Wheel Incorporating a Nitroxide Motif // Chem.-Eur. J. 2018. Vol. 24, № 5. P. 1198–1203.

The synthesis of the new nitroxide crown ether 8 and its use as the wheel in a bistable [2]rotaxane, containing dialkylammonium and 4,4'-bipyridinium recognition sites, is reported. The synthesis of 8 was achieved by the sequential addition of substituted phenyl groups to a nitrone derivatives leading to the preferential formation of the cis stereoisomer. Due to charge-dipole interactions between the nitroxide unit and the bipyridinium moiety, it was possible to probe the movement of the macrocycle between the two molecular stations of the [2]rotaxane after addition of a base by measuring the nitrogen hyperfine splitting in the corresponding EPR spectra. The equilibrium constant for the complexation of dibenzyl viologen by the macrocycle 8 was also determined by EPR titration.


4. Bols P.S., Anderson H.L. Shadow Mask Templates for Site-Selective Metal Exchange in Magnesium Porphyrin Nanorings // Angew. Chem.-Int. Edit. 2018. Vol. 57, № 26. P. 7874–7877.

Molecular templates can be used in many different ways to control the outcome of chemical reactions. Herein, we present a new type of template-directed synthesis. We show that templates can be used as shadow masks: The shape of the template becomes imprinted on the product because reactions only occur at sites not masked by the template. We demonstrate this effect by using oligopyridine templates to dictate the sites of demetalation when a magnesium porphyrin nanoring is treated with acid. Magnesium centers that are coordinated to the template are protected whereas uncoordinated magnesium centers are removed. After site-selective demtetalation, the template can be removed, and other cations, such as zinc(II) and copper(II), can be inserted into the free-base porphyrin centers. This strategy provides a simple route to a wide range of heterometalated porphyrin arrays.


5. Camp A.M. et al. Mapping the Binding Modes of Hemilabile Pincer Crown Ether Ligands in Solution Using Diamagnetic Anisotropic Effects on NMR Chemical Shift // Inorg. Chem. 2017. Vol. 56, № 18. P. 11141–11150.

A protocol for identifying ligand binding modes in a series of iridium pincer complexes bearing hemilabile aza-crown ether ligands has been developed using readily accessible NMR methods. The approach was tested on a collection of 13 structurally diverse pincercrown ether complexes that include several newly characterized species. New synthetic routes enable facile interconversion of coordination modes and supporting ligands. Detailed structural assignments of five complexes reveal that the difference in chemical shift (Delta delta) between geminal protons in the crown ether is influenced by diamagnetic anisotropy arising from halides and other ligands in the primary coordination sphere. The average difference in chemical shift between diastereotopic geminal protons in the crown ether macrocycle (Delta delta(avg)), as determined through a single H-1-C-13 HSQC experiment, provides information on the pincer ligand binding mode by establishing whether the macrocycle is in close proximity to the metal center. The Delta delta(avg) values for binding modes that involve chelating ether(s) bound to iridium are roughly 2-fold larger than those for tridentate complexes with no Ir-O bonds.


6. Cardenas-Jiron G.I., Leon-Plata P., Seminario J.M. Functionalized Graphene and Cobalt Phthalocyanine Based Materials with Potential Use for Electrical Conduction / ed. Seminario J.M. Dordrecht: Springer, 2014. Vol. 16.

In this work we investigate at the density functional theory level (B3PW91, B3LYP, M05-2X) the electrical properties of complexes formed by cobalt phthalocyanine (CoPc) and cobalt tetraaminophthalocyanine (CoTAPc) adsorbed on functionalized graphene (FG). As functionalization are studied the carboxylate (18 complexes), epoxide (three complexes), hydroxyl (three complexes) and carboxyl (two complexes) groups. Three models of graphene molecules are used; pristine, defect (Def), and vacancy (Vac), leading to a total of 26 complexes. We studied three main orientations for the interaction graphene-phthalocyanine; parallel, perpendicular and extended. Binding energies show a very large stability for G-COO--CoTAPc complexes (similar to-100 to -150 kcal/mol) in an extended orientation and a little lower for G-O-CoPc and G-OH-CoPc in a parallel orientation (similar to-20 to -65 kcal/mol). No adsorption of CoPc occur on G-COOH. HOMO-LUMO Gap (HLG) show higher values for the complexes than the fragment FG when the functionalization COO-is by the edge of graphene; giving account of a favorable adsorption of CoPc (CoTAPc) in agreement with the binding energies. For epoxide and hydroxyl (except for G-Vac) where the functionalization is on the center of G, we found that HLG is shorter in similar to 0.5 eV with respect to FG (similar to 4 eV). The high HLG values for these complexes suggest that the adsorption of CoPc is completely favorable. Several of these complexes present an electron acceptor species (FG) and an electron donor species (CoPc, CoTAPc). For the stable complexes, we found a higher current conduction for the parallel orientation. Thus, complexes with carboxylate functionalization present a conduction of similar to 7 mu A similar for hydroxyl (similar to 7 mu A) but some lower than for epoxide (similar to 18 mu A). The results have shown that the adsorption of cobalt phthalocyanines on functionalized graphene is feasible; yielding a tunable hybrid material that allows sensing because of the intrinsic electrical properties provided by functionalized G and CoPc.

7. Chen L. et al. High-throughput and selective solid-phase extraction of urinary catecholamines by crown ether-modified resin composite fiber // J. Chromatogr. A. 2018. Vol. 1561. P. 48–55.

In the present study, we developed a simple and high-throughput solid phase extraction (SPE) procedure for selective extraction of catecholamines (CAs) in urine samples. The SPE adsorbents were electro-spun composite fibers functionalized with 4-carboxybenzo-18-crown-6 ether modified XAD resin and polystyrene, which were packed into 96-well columns and used for high-throughput selective extraction of CAs in healthy human urine samples. Moreover, the extraction efficiency of packed-fiber SPE (PFSPE) was examined by high performance liquid chromatography coupled with fluorescence detector. The parameters affecting the extraction efficiency and impurity removal efficiency were optimized, and good linearity ranging from 0.5 to 400 ng/mL was obtained with a low limit of detection (LOD, 0.2-0.5 ng/mL) and a good repeatability (2.7%-3.7%, n= 6). The extraction recoveries of three CAs ranged from 70.5% to 119.5%. Furthermore, stable and reliable results obtained by the fluorescence detector were superior to those obtained by the electrochemical detector. Collectively, PFSPE coupled with 96-well columns was a simple, rapid, selective, high-throughput and cost-efficient method, and the proposed method could be applied in clinical chemistry. (C) 2018 Elsevier B.V. All rights reserved.


8. Cnossen A., Roche C., Anderson H.L. Scavenger templates: a systems chemistry approach to the synthesis of porphyrin-based molecular wires // Chem. Commun. 2017. Vol. 53, № 75. P. 10410–10413.

A hexa-pyridyl template can be used as a scavenger to facilitate the synthesis of a linear porphyrin dodecamer from a mixture of linear hexamers with one or two terminal reactive groups. The template suppresses polymer formation by rapidly cyclizing the fully deprotected hexamer, thus up-regulating formation of the linear dodecamer.


9. Donoghue C.S.J.N.O.Q., Fomo G., Nyokong T. Electrode Modification Using Alkyne Manganese Phthalocyanine and Click Chemistry for Electrocatalysis // Electroanalysis. 2016. Vol. 28, № 12. P. 3019–3027.

In this work, azidobenzene diazonium salt is grafted onto a glassy carbon electrode (GCE) followed by clicking of manganese tetrahexynyl phthalocyanine for the electrocatalysis of hydrazine. The GCE was first grafted via the in situ diazotization of a diazonium salt, rendering the GCE surface layered with azide groups. From this point, the 1,3-dipolar cycloaddition reaction, catalyzed by a copper catalyst was utilized to 'click' the manganese tetrahexynyl phthalocyanine to the surface of the grafted GCE. This new platform was then characterized using cyclic voltammetry (CV), scanning electrochemical microscopy (SECM) and X-ray photoelectron spectroscopy (XPS). Based on the cyclic voltammetry calibration curve of electrocatalysis for hydrazine, the clicked Mn phthalocyanine electrode proved to be an effective sensor with a sensitivity of 27.38 mu A mM(-1) and the limit of detection (LoD) of 15.4 pM which is a great improvement compared to other reported sensors for this analyte.


10. Fidan I. et al. Revisiting the Ullman’s Radical Chemistry for Phthalocyanine Derivatives // Chem.-Eur. J. 2018. Vol. 24, № 20. P. 5359–5365.

Phthalocyanine derivatives do not cease to gain attention due to their numerous properties and applications (e.g., sensor, PDT). This makes them a unique scaffold for the design of new material. In this context, we were interested to develop the synthesis of an imino nitroxide-substituted phthalocyanine by Ullman's procedure; a challenge due to the intrinsic low solubility of most phthalocyanine derivative in much solvents. To overcome this solubility problem, we designed a phthalocyanine with bulky neopentyl substituents in peripheral positions as counterpart to the imino nitroxide moieties. The imino nitroxide-substituted phthalocyanine was obtained by condensation of a monoformyl-substituted phthalocyanine with 2,3-bis(hydroxylamino)-2,3-dimethylbutane in refluxing THF-MeOH (2:1) mixture in the presence of p-toluenesulfonic acid monohydrate, follow by oxidation with PbO2. Characterization was performed by electrochemistry, UV/Vis and EPR spectroscopy in solution as well as SQUID in solid state.


11. Franski R., Ogorek K., Gierczyk B. Formation of organometallic species from complexes of N-phenylaza-crown ether conjugates with lead cations in CID-MS/MS conditions // Int. J. Mass Spectrom. 2017. Vol. 421. P. 164–169.

Gas phase decomposition of the ions [M + PbNO3](+) (M stands for fluoro-substituted N-nitrophenylazacrown ether conjugate), has been studied by the electrospray ionization-collision induced dissociation tandem mass spectrometry (ESI-CID-MS/MS). The conjugates containing hydrogen atom at ortho position to the crown moiety, form abundant fragment ions which can be assigned as complexes of deprotonated conjugates and lead cation, thus the ions [M - H+ Pb](+) (fragment ions formed as a result of HNO3 loss). Interaction between the nitro group (present at the second ortho position to the crown moiety) and the metal cation affects the formation of fragment ion [M - H+ Pb](+) (but does not prevent its formation). Ions [M - H + Pb](+) are very rare example of the organometallic species (containing metal-carbon bond), in which metal cation is also complexed by crown ether moiety. (C) 2017 Elsevier B.V. All rights reserved.


12. Fujihara A., Sato T., Hayakawa S. Enantiomer-selective ultraviolet photolysis of temperature-controlled protonated tryptophan on a chiral crown ether in the gas phase // Chem. Phys. Lett. 2014. Vol. 610. P. 228–233.

Enantiomer-selective ultraviolet photolysis of temperature-controlled protonated tryptophan (TrpH(+)) on the chiral crown ether, (+)-(18-crown-6)-2,3,11,12-tetracarboxylic acid (18C6TA), was examined using a tandem mass spectrometer containing a temperature-variable 22-pole ion trap. The spectra of D-TrpH(+)-(+)-18C6TA at 9-320 K showed that the loss of NH2CH2COOH due to C-alpha-C-beta bond cleavage decreased gradually with increasing temperature. The spectrum at room temperature was similar to that of L-TrpH(+)-(+)-18C6TA, which showed no temperature dependence on photolysis. The chiral-specific photolysis of cold D-TrpH(+)-(+)-18C6TA was attributed to the structures involving the chiral-dependent interactions of the C-alpha-H group of TrpH(+) with the oxygen atoms of (+)-18C6TA. (C) 2014 Elsevier B.V. All rights reserved.


13. Goeth M. et al. Gas-phase microsolvation of ubiquitin: investigation of crown ether complexation sites using ion mobility-mass spectrometry // Analyst. 2016. Vol. 141, № 19. P. 5502–5510.

In this study the gas-phase structure of ubiquitin and its lysine-to-arginine mutants was investigated using ion mobility-mass spectrometry (IM-MS) and electron transfer dissociation-mass spectrometry (ETD-MS). Crown ether molecules were attached to positive charge sites of the proteins and the resulting non-covalent complexes were analysed. Collision induced dissociation (CID) experiments revealed relative energy differences between the wild type and the mutant crown-ether complexes. ETD-MS experiments were performed to identify the crown ether binding sites. Although not all of the binding sites could be revealed, the data confirm that the first crown ether is able to bind to the N-terminus. IM-MS experiments show a more compact structure for specific charge states of wild type ubiquitin when crown ethers are attached. However, data on ubiquitin mutants reveal that only specific lysine residues contribute to the effect of charge microsolvation. A compaction is only observed for one of the investigated mutants, in which the lysine has no proximate interaction partner. On the other hand when the lysine residues are involved in salt bridges, attachment of crown ethers has little effect on the structure.


14. Gregor L.C. et al. Salt-promoted catalytic methanol carbonylation using iridium pincer-crown ether complexes // Catal. Sci. Technol. 2018. Vol. 8, № 12. P. 3133–3143.

Iridium complexes of pincer ligands containing aza-crown ether macrocycles are precatalysts for methanol carbonylation. Eleven different pincer complexes were examined in the presence of various potential external promoters under standard reaction conditions of 0.1 M CH3I and 0.34 mM catalyst in methanol under 25 bar CO and heated to 150 degrees C for 3 hours. Methyl acetate is the major product under these conditions, with turnover numbers (TONs) for all acetyl-containing products ranging from 265 to 1950 based on the choice of metal salt (with LiCl and HfCl4 giving highest TON) or tetrabutylammonium salts. While the pincer-crown ether complexes remain intact under conditions of low temperature and pressure, the precatalysts convert to new active species derived from pincer ligand methanolysis in high pressure reactors with excess methyl iodide.


15. Hansen C.B., Filatov A.S., Hillhouse G.L. Crystal structure of the inverse crown ether tetrakis[mu(2)-bis(trimethylsilyl)amido]-mu(4)-oxido-dicobalt(II)disodiu m, [Co2Na2{mu(2)-N(SiMe3)(2)}(4)]-(mu(4)-O) // Acta Crystallogr. Sect. E.-Crystallogr. Commun. 2016. Vol. 72. P. 780–+.

The title compound, [Co2Na2{mu(2)-N(SiMe3)(2)}(4)](mu(4)-O), (I), represents a new entry in the class of inverse crown ethers. In the molecule, each Co atom is formally in the oxidation state +II. The structure contains one half of a unique molecule per asymmetric unit with the central mu(4)-oxido ligand residing on an inversion center, leading to a planar coordination to the Na and Co atoms. In the crystal, bulky trimethylsilyl substituents prevent additional interactions with cobalt. However, weak intermolecular Na center dot center dot center dot H3C-Si interactions form an infinite chain along [010]. The structure is isotypic with its Mg, Mn and Zn analogues.


16. Higashino T. et al. Fusing Porphyrins and Phospholes: Synthesis and Analysis of a Phosphorus-Containing Porphyrin // Angew. Chem.-Int. Edit. 2016. Vol. 55, № 40. P. 12311–12315.

A phosphole-fused porphyrin dimer, as a representative of a new class of porphyrins with a phosphorus atom, was synthesized for the first time. The porphyrin dimer exhibits remarkably broadened absorption, indicating effective pi-conjugation over the two porphyrins through the phosphole moiety. The porphyrin dimer possesses excellent electron-accepting character, which is comparable to that of a representative electron-accepting material, [60]PCBM. These results provide access to a new class of phosphorus-containing porphyrins with unique optoelectronic properties.


17. Hipps K.W., Mazur U. Kinetic and Thermodynamic Control in Porphyrin and Phthalocyanine Self-Assembled Monolayers // Langmuir. 2018. Vol. 34, № 1. P. 3–17.

Porphyrins and phthalocyanines are ubiquitous in modern science and technology. Their stability, redox properties, and photoresponse make them candidates for numerous applications. Many of these applications rely on thin films, and these are critically dependent on the first monolayer. In this article, we focus on noncovalently bound self-assembled monolayers of porphyrins and phthalocyanines at the solution-solid interface with special emphasis on the kinetic and thermodynamic processes that define the films and their reaction chemistry. We first discuss the difference between film-formation kinetics and desorption kinetics from fully formed films. We then present evidence that many of these monolayers are controlled by adsorption kinetics and are not in thermodynamic equilibrium. Measurement of the solution-solid interface desorption energy by scanning tunneling microscopy is discussed, and data is presented for cobalt, nickel, and free base octaethylporphyrin. The activation energy for the desorption of these compounds into phenyloctane is about half of the computed desorption energy in vacuum, and this is discussed in terms of the role of the solvent. Preexponential factors are very low compared to desorption into vacuum, and this is attributed to a reduction in the entropy of activation due to the participation of solvent in the transition state. An example of the use of relative desorption kinetics to create a new binary surface structure is given. It is suggested that this is a synthesis route that may have been missed because of the large difference in solution concentrations required to drive binary film formation. Attention then turns to the axial reaction chemistry of metalloporphyrins and metallophthalocyanines supported on conducting surfaces. We show several examples of chemistry unique to the supported complexes: cases where the metal binds ligands more readily and cases where the substrate induces ligand loss. Understanding this new axial coordination chemistry is of great importance in catalysis, sensing, and the growth of 3D materials from a self-assembled template.


18. Hod I. et al. Fe-Porphyrin-Based Metal-Organic Framework Films as High-Surface Concentration, Heterogeneous Catalysts for Electrochemical Reduction of CO2 // ACS Catal. 2015. Vol. 5, № 11. P. 6302–6309.

Realization of heterogeneous electrochemical CO2-to-fuel conversion via molecular catalysis under high-flux conditions requires the assembly of large quantities of reactant-accessible catalysts on conductive surfaces. As a proof of principle, we demonstrate that electrophoretic deposition of thin films of an appropriately chosen metal-organic framework (MOF) material is an effective method for immobilizing the needed quantity of catalyst. For electrocatalytic CO2 reduction, we used a material that contains functionalized Fe-porphyrins as catalytically competent, redox-conductive linkers. The approach yields a high effective surface coverage of electrochemically addressable catalytic sites (similar to 10(15) sites/cm(2)). The chemical products of the reduction, obtained with similar to 100% Faradaic efficiency, are mixtures of CO and H-2. These results validate the strategy of using MOF chemistry to obtain porous, electrode-immobilized, networks of molecular catalysts having competency for energy-relevant electrochemical reactions.


19. Hu S.-X. et al. Periodic Trends in Actinyl Thio-Crown Ether Complexes // Inorg. Chem. 2018. Vol. 57, № 5. P. 2899–2907.

In-cavity complexes and their bonding features between thio-crown (TC) ethers and f-elements are unexplored so far. In this paper, actinyl(VI) (An = U, Np, Pu, Am, and Cm) complexes of TC ethers have been characterized using relativistic density functional theory. The TC ether ligands include tetrathio-12-crown-4 (12TC4), pentathio-15-crown-5 (15TC5), and hexathio-18-crown-6 (18TC6). On the basis of the calculations, it is found that the "double-decker" sandwich structure of AnO(2)(12TC4)(2)(2+) and "side-on" structure AnO(2)(12TC4)(2+) are changed to "insertion" structures for AnO(2)(15TC5)(2+) and AnO(2)(18TC6)(2+). due to increased size of the TC ether ligands. The actinyl monocyclic TC ether complexes are found to exhibit conventional conformations, with typical An-O-actinyl and An-S-ligand distances and angles. Chemical bonding analyses by Weinhold's natural population analysis (NPA), natural localized molecular orbital (NLMO), and energy decomposed analysis (EDA), show that a typical ionic An-S-ligand bond with the extent of covalent interaction between the An and S atoms primarily attributable to the degree of radial distribution of the S 3p atomic orbitals. The similarity and difference of the oxo-crown and TC ethers as ligands for actinide coordination chemistry are discussed. As soft S-donor ligands, TC ethers may be candidate ligands for actinide recognition and extraction.


20. Jadhav V.H. et al. Crown ether metal complex fluoride salt as a facile and low hygroscopic fluoride source for nucleophilic fluorination // Chem. Eng. J. 2015. Vol. 270. P. 36–40.

A variety of crown ether metal complex fluorides (CEMCFs), such as [18-C-6K][F], [18-C-6Cs][F], [18-C-6Rb][F], and [18-C-6Na][F] ([18-C-6K] = 18-crown-6 potassium cation complex; [18-C-6Cs] = 18-crown-6 cesium cation; [18-C-6Rb] = 18-crown-6 rubidium cation; [18-C-6Na] = 18-crown-6 sodium cation; [F] = fluoride), were prepared in quantitative yields by simply treating the correct molar ratio of 18-crown-6 with the corresponding alkali metal fluorides at 25 degrees C for 24 h in water after evaporation and vacuum drying. In particular, [18-C-6K][F] exhibited relatively low hygroscopic properties compared with the conventional tetrabutylammonium fluoride (TBAF). The efficiency of these CEMCFs as a fluoride source was examined in various nucleophilic fluorination reactions. The results showed that these CEMCFs had good reactivity except for [18-C-6Na][F]. Furthermore, tert-alcohol media enhanced the reactivity and chemo-selectivity of [18-C-6K][F] significantly in the nucleophilic fluorination of base-sensitive substrates. In addition, [18-C-6K][F] showed good performance in the selective phenolic desilylation of bis-TBDMS ether in methanol. (C) 2015 Elsevier B.V. All rights reserved.


21. Jiang X., Jiang Z., Zhao J. Self-assembly 2D zinc-phthalocyanine heterojunction: An ideal platform for high efficiency solar cell // Appl. Phys. Lett. 2017. Vol. 111, № 25. P. 253904.

As an alternative to silicon-based solar cells, organic photovoltaic cells emerge for their easy manufacture, low cost, and light weight but are limited by their less stability, low power conversion efficiencies, and low charge carrier mobilities. Here, we design a series of two-dimensional (2D) organic materials incorporating zinc-phthalocyanine (ZnPc) based building blocks which can inherit their excellent intrinsic properties but overcome those shortcomings. Our first-principles calculation shows that such 2D ZnPc-based materials exhibit excellent thermal stabilities, suitable bandgaps, small effective masses, and good absorption properties. The additional benzene rings and nitrogen atoms incorporated between ZnPc molecules are mainly responsible for the modifications of electronic and optical properties. Moreover, some heterojunction solar cells constructed using those 2D ZnPc monolayers as the donor and acceptor have an appropriate absorber gap and interface band alignment. Among them, a power conversion efficiency up to 14.04% is achieved, which is very promising for the next-generation organic solar cells. Published by AIP Publishing.


22. Jyothi R.K., Lee J.-Y. The role of macrocyclic compounds in the extraction and possible separation of platinum and rhodium from chloride solutions // Sci Rep. 2016. Vol. 6. P. 27668.

Macrocyclic compounds (crown ethers), specifically 18-crown-6 (18-C-6), benzo-15-crown-5 (B-15-C-5), di-benzo-18-crown-6 (DB-18-C-6) and di-cyclohexano-18-crown-6 (DC-18C-6), are used as extractants as well as synergists with amine-group extractants. Platinum and rhodium belong to platinum-group metals (PGMs) and have very similar ionic radii and similar properties. The separation of PGMs is most useful for the preparation of functional materials. Macrocyclic compounds are tested for platinum and rhodium separation and are found to achieve marginal separation. Amines (used as extractants) are paired with macrocyclic compounds (used as synergists), and the separation factor between platinum and rhodium is increased with synergistic enhancement from a chloride solution. The present study discusses extraction chemistry, separation factors and the synergy between platinum and rhodium from chloride solutions. To ensure accurate data, the aqueous samples in this study are analyzed using an inductively coupled plasma optical emission spectrometer (ICP-OES).


23. Kang D. et al. Dual role of Cu2O nanocubes as templates and networking catalysts for hollow and microporous Fe-porphyrin networks // Chem. Commun. 2017. Vol. 53, № 17. P. 2598–2601.

Cu2O nanocubes were used for the synthesis of hollow and microporous Fe porphyrin networks (H-MFePN). In this synthesis, Cu2O nanocubes performed not only as networking catalysts but also as shape controlling templates. MFePNwere formed on the surface of the Cu2O nanocubes through azide-alkyne cycloaddition of tetrakis(4-ethynylphenyl) Fe-porphyrin with 1,4-diazidobenzene. H-MFePN showed excellent catalytic activities in carbene insertion into N-H bonds, maintaining their activities during five recycle tests.

24. Kinjo K. et al. Supramolecular Porphyrin Copolymer Assembled through Host-Guest Interactions and Metal-Ligand Coordination // Angew. Chem.-Int. Edit. 2015. Vol. 54, № 49. P. 14830–14834.

Bisporphyrin cleft molecule 1Zn possessing a guest moiety assembled to form supramolecular polymers through host-guest interactions. Bispyridine cross-linkers created interchain connections among the supramolecular polymers to form networked polymers in solution. Solution viscometry confirmed that the cross-linked supramolecular polymers were highly entangled. Frequency-dependent linear viscoelastic spectroscopy revealed that the supramolecular polymers generated well-entangled solutions with associating and networking polymers, whereas the solid-like aggregates moved individually without breaking and reforming structures below the transition temperature of 9.6 degrees C. Morphological transition of the supramolecular polymers was evidenced by AFM images; the non-cross-linked polymer resulted in wide-spread thin networks, while the cross-linked networks produced thicker worm-like nanostructures. The supramolecular networks gelled in 1,1,2,2-tetrachloroethane, and an elastic freestanding film was fabricated with a Young's modulus of1 GPa.


25. Lee S.-S. et al. Computational study of S(N)2 reactions promoted by crown ether: Contact ion pair versus solvent-separated ion pair mechanism // Int. J. Quantum Chem. 2018. Vol. 118, № 11. P. e25547.

We examined by quantum chemical methods the mechanism of S(N)2 reaction using metal bromide MBr (M=Na, K, Cs) and KX (X= F, Cl) in CH3CN promoted by crown ether (18-crown-6). We focus on whether the metal salts react as a contact ion pair (CIP; M+ and X- in close contact) or as a solvent-separated ion pair (SSIP; M+ and X- at large distance). In SSIP mechanism, X- is removed far enough from M+ for the metal salt to be considered as separated by the effects of the crown ether and the solvent. In the CIP picture, conversely, the coordination of 18-crown-6 to M+ is not sufficient to overcome the powerful Coulombic interactions between M+ and X-. We find that the CIP route is favored for S(N)2 bromination processes using MBr (M=Na, K, Cs). For S(N)2 reaction using KF, the feasibility of the two pathways is essentially equal, whereas for S(N)2 chlorination by KCl the SSIP route is predicted to be favored.


26. Legnani L., Morandi B. Direct Catalytic Synthesis of Unprotected 2-Amino-1-Phenylethanols from Alkenes by Using Iron(II) Phthalocyanine // Angew. Chem.-Int. Edit. 2016. Vol. 55, № 6. P. 2248–2251.

Aryl-substituted amino alcohols are privileged scaffolds in medicinal chemistry and natural products. Herein, we report that an exceptionally simple and inexpensive Fe-II complex efficiently catalyzes the direct transformation of simple alkenes into unprotected amino alcohols in good yield and perfect regioselectivity. This new catalytic method was applied in the expedient synthesis of bioactive molecules and could be extended to aminoetherification.


27. Lu G. et al. Europium Triple-Decker Complexes Containing Phthalocyanine and Nitrophenyl-Corrole Macrocycles // Inorg. Chem. 2015. Vol. 54, № 18. P. 9211–9222.

A series of europium triple-decker complexes containing phthalocyanine and nitrophenyl-corrole macrocycles were synthesized and characterized by spectroscopic and electrochemical methods in nonaqueous media. The examined compounds are represented as Eu-2[Pc(OC4H9)(8)](2)[Cor(Ph)(n)(NO2Ph)(3-n)], where n varies from 0 to 3, Pc(OC4H9)(8) represents the phthalocyanine macrocycle, and Cor indicates the corrole macrocyde having phenyl (Ph) or nitrophenyl (NO2Ph) meso substituents. Three different methods were used for syntheses of the target complexes, two of which are reported here for the first time. Each examined compound undergoes five reversible one-electron oxidations and 3-5 one-electron reductions depending upon the number of NO2Ph substituents. The nitrophenyl groups on the meso positions of the corrole are highly electron-withdrawing, and this leads to a substantial positive shift in potential for the five oxidations and first reduction in CH2Cl2, PhCN, or pyridine as compared to the parent triple-decker compound with a triphenylcorrole macrocycle. The measured E-1/2 values are linearly related to the number of NO2Ph groups on the corrole, and the relative magnitude of the shift in potential for each redox reaction was used in conjunction with the results from thin-layer spectro-electrochemistry to assign the initial site of oxidation or reduction on the molecule. The nitrophenyl substituents are also redox-active, and each is reduced to [C6H4NO2](-) in a separate one-electron transfer step at potentials between -1.12 and -1.42 V versus saturated calomel electrode.


28. Moons H. et al. Photoreduction and light-induced triplet-state formation in a single-site fluoroalkylated zinc phthalocyanine // Dalton Trans. 2014. Vol. 43, № 40. P. 14942–14948.

Electron-withdrawing perfluoroalkyl peripheral substituents enhance the photosensitizing properties of metal phthalocyanines while increasing their solubility, thus providing opportunities for advanced characterization of their catalytically-relevant excited states. Optical absorption and electron paramagnetic resonance (EPR) spectroscopy experiments reveal that red light induces the reduction of perfluoroisopropyl-substituted zinc(II) phthalocyanine (F64PcZn) dissolved in ethanol. A similar photoreduction does not occur in toluene. Furthermore, intense UV irradiation causes the photodegradation of F64PcZn in ethanol, but low power UV illumination favours the formation of the triplet excited state, a prerequisite for new photocatalytic applications. The UV-induced triplet state of F64PcZn is characterized using a combination of transient EPR experiments and DFT computations.


29. Namgoong J.W. et al. Improving nanoparticle dispersions of pigment and its application to a color filter: New phthalocyanine derivatives as synergist // J. Ind. Eng. Chem. 2018. Vol. 58. P. 266–277.

Four synergists were synthesized to enhance pigment nanoparticles dispersion and the contrast ratio. The interaction between the synergist and the dispersant was confirmed by infra-red (IR) spectrometry. We demonstrate that the hydrogen bonds forming between the synergist and the dispersant act as a key factor. To analyze the dispersion properties, dynamic light scattering (DLS), and electron microscopic analysis was examined. The spectral and color characteristics was also measured by UV-vis spectrometry and colorimetry, and the contrast ratio of color filters was evaluated. This study confirms that the prepared synergist can increase the contrast ratio of green color filter. (C) 2017 The Korean Society of industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.


30. Nxele S.R., Nyokong T. Conjugation of Azide-functionalised CdSe/ZnS Quantum Dots with Tetrakis(5-hexyn-oxy) Fe(II) phthalocyanine via Click Chemistry for Electrocatalysis // Electrochim. Acta. 2016. Vol. 194. P. 26–39.

In this work, azide-funtionalised CdSe/ZnS QDs are conjugated with tetrakis(5-hexyn-oxy) Fe(II) phthalocyanine for the electrocatalytic detection of paraquat. The conjugate was fully characterised using various techniques to confirm the success of the reaction. They also showed good electrocatalytic ability towards the electroreduction of paraquat with limits of detection (LoD) of 5.9 x 10(-9) mu M which is a great improvement compared to other reported sensors for this analyte. (C) 2016 Elsevier Ltd. All rights reserved.


31. Pan Y. et al. Scanning tunnelling spectroscopy and manipulation of double-decker phthalocyanine molecules on a semiconductor surface // J. Phys.-Condes. Matter. 2017. Vol. 29, № 36. P. 364001.

A scanning tunnelling microscope (STM) operated at 5 K was used to study dysprosium biphthalocyanine (DyPc2) molecules adsorbed on the inert III-V semiconductor surface InAs(111) A. Orbital imaging and scanning tunnelling spectroscopy measurements reveal that the molecular electronic structure remains largely unperturbed, indicating a weak moleculesurface binding. The molecule adsorbs at the In vacancy site of the (2 x 2)-reconstructed surface and is highly sensitive to current-induced excitations leading to random rotational fluctuations. Owing to the weak surface binding, individual molecules can be precisely repositioned and arranged by the STM tip via attractive tip-molecule interaction. In this way, DyPc2 dimers of well-defined internal structure can be assembled which exist in two conformations of equivalent appearance. A binary switching between these two conformers can be induced by injecting electrons into one of the two molecules. The conformational change of the dimer proceeds via a concerted molecular rotation and minor lateral displacement. The synchronised switching observed here is attributed to steric interactions between the two molecules constituting the dimer.


32. Patil R.S. et al. Formation of Water Channels in the Crystalline Hydrates of Macrocyclic Compounds // Chem.-Eur. J. 2018. Vol. 24, № 13. P. 3299–3304.

Crystalline hydrates of macrocyclic compounds such as pyroagllol[4] arenes (PgCs) and resorcin[ 4] arenes ( RsCs) are rare owing to their lower water solubility. Functionalization of these macrocyclic compounds is an affordable way to enhance water solubility. However, functionalization also encounters the formation of multiple conformers and subsequent difficulty in purification of the product. Herein, four novel crystalline hydrates of functionalized PgCs and RsCs were synthesized. Formation of water channels and the effects of intermolecular interactions on the physical properties of these novel hydrates are discussed.


33. Pereira T.L. et al. Optimally tuned functionals improving the description of optical and electronic properties of the phthalocyanine molecule // J. Mol. Model. 2017. Vol. 23, № 3. P. 71.

By means of Density functional theory and time-dependent density functional theory calculations, we present a comprehensive investigation on the influence of different functional schemes on electronic and optical properties of the phthalocyanine molecule. By carrying out our own tuning on the OT-LC-BLYP/6-31G(d,p) functional, we show that such a procedure is fundamental to accurately match experimental results. We compare our results to several others available in the literature, including the B3LYP/6-31+G(d,p) set, which is commonly portrayed as the best combination in order to obtain a good description of the band gap. The results obtained here present not only significant improvement of the optical properties from the conventional BLYP, but we can also objectively report an improvement of our tuned functional when compared to the current benchmark of the literature as far as optical properties are concerned. Particularly, by means of this approach, it was possible to achieve a good agreement between the theoretical and experimental optical gap as well as the positioning of the main peaks in the absorption spectrum. Our results thus suggest that correcting the long-range term on exchange term of the Coulomb operator, by means of a tuning procedure, is a good option to accurately describe properties of the phthalocyanine molecule.


34. Pires S.M.G. et al. Oxidation of organosulfur compounds using an iron(III) porphyrin complex: An environmentally safe and efficient approach // Appl. Catal. B-Environ. 2014. Vol. 160. P. 80–88.

Following our approach on the use of metalloporphyrins as catalysts and hydrogen peroxide as oxidant in the oxidation of organosulfur compounds (e.g. sulfides, benzothiophenes and dibenzothiophenes), herein the excellent catalytic performance of a homogeneous iron(III) porphyrin complex is demonstrated. Beyond the better results obtained, when compared with those with manganese(III) complexes, the present procedure involves a cleaner approach because ethanol is used as solvent and a co-catalyst is not required. For all the studied substrates (1-10), conversions higher than 95% were achieved with Fe(TF4NMe2PP)Cl (I). More significantly, catalyst (I) is also efficient in the oxidation of a model fuel, constituted by a mixture of benzothiophene (3), 3-methylbenzothiophene (5), 4-methyldibenzothiophene (8) and 4,6-diethyldibenzothiophene (10) in hexane, affording an overall conversion of 84%. (C) 2014 Elsevier B.V. All rights reserved.


35. Rioz-Martinez A. et al. DNA-Accelerated Catalysis of Carbene-Transfer Reactions by a DNA/Cationic Iron Porphyrin Hybrid // Angew. Chem.-Int. Edit. 2016. Vol. 55, № 45. P. 14136–14140.

A novel DNA-based hybrid catalyst comprised of salmon testes DNA and an iron(III) complex of a cationic meso-tetrakis(N-alkylpyridyl)porphyrin was developed. When the N-methyl substituents were placed at the ortho position with respect to the porphyrin ring, high reactivity in catalytic carbene-transfer reactions was observed under mild conditions, as demonstrated in the catalytic enantioselective cyclopropanation of styrene derivatives with ethyl diazoacetate (EDA) as the carbene precursor. A remarkable feature of this catalytic system is the large DNA-induced rate acceleration observed in this reaction and the related dimerization of EDA. It is proposed that high effective molarity of all components of the reaction in or near the DNA is one of the key contributors to this unique reactivity. This study demonstrates that the concept of DNA-based asymmetric catalysis can be expanded into the realm of organometallic chemistry.


36. Salman A.A. et al. Functional glycolipid-crown-ethers by click chemistry // Carbohydr. Res. 2015. Vol. 406. P. 41–45.

A series of glycolipid crown ether analogs was prepared by bis-propargylation of lauryl glycoside followed by subsequent click-coupling with ethylene glycol-based diazides. The triazole-linked macrocycles were obtained in remarkable high yields. While the surfactant assembly was affected by presence of sodium ions, suggesting the formation of complexes, no ion-selectivity was observed for the macrocylic ligands. Computational studies suggest a low but significant cation-binding activity of the macrocycle, involving coordination at both oxygen and nitrogen atoms. (C) 2015 Elsevier Ltd. All rights reserved.


37. Sekita M. et al. Intense Ground-State Charge-Transfer Interactions in Low-Bandgap, Panchromatic Phthalocyanine-Tetracyanobuta-1,3-diene Conjugates // Angew. Chem.-Int. Edit. 2016. Vol. 55, № 18. P. 5560–5564.

A cycloaddition-retroelectrocyclization reaction between tetracyanoethylene and two zinc phthalocyanines (Zn(II)Pcs) bearing one or four anilino-substituted alkynes has been used to install a strong, electron-accepting tetracyanobuta-1,3-diene (TCBD) between the electron-rich (ZnPc)-Pc-II and aniline moieties. A combination of photophysical, electrochemical, and spectroelectrochemical investigations with the (ZnPc)-Pc-II-TCBD-aniline conjugates, which present panchromatic absorptions in the visible region extending all the way to the near infrared, show that the formal replacement of the triple bond by TCBD has a dramatic effect on their ground- and excited-state features. In particular, the formation of extremely intense, ground-state charge-transfer interactions between (ZnPc)-Pc-II and the electron-accepting TCBD were observed, something unprecedented not only in Pc chemistry but also in TCBD-based porphyrinoid systems.


38. Sen B.N. et al. Synthesis and characterization of terminalalkynyl-substituted unsymmetrical zinc phthalocyanine conjugated with well-defined polymers // Dyes Pigment. 2014. Vol. 100. P. 1–10.

Synthesis of unsymmetrically terminalalkynyl substituted zinc (II) phthalocyanine (ZnPc) through an efficient statistical condensation reaction with the unprotected phthalonitrile (2) is reported for the first time. Isolated ZnPc bearing one terminalalkynyl group is a good precursor for Cu(I)-catalyzed azide-alkyne 1,3-dipolar cycloaddition (CuAAC) reaction which is classified under the term "click chemistry". This was approved by the successful click reaction between ZnPc and azide end-functional well-defined polymers obtained by atom transfer radical polymerization (ATRP), and consecutive azidation of corresponding bromo end-functional polymers. The click-reaction efficiencies for the formation of Pc-end functional poly(tert-butyl acrylate) (PtBA), and polystyrene (PS) have been found to be 75, 93% respectively. Functionalization of ZnPc with PS increased the chemical stability of the complex but decreased the electrochemical reversibility during redox reactions. In-situ electrocolorimetric measurements of the complexes allowed the quantification of color coordinates of the each electrogenerated anionic and cationic redox species. (C) 2013 Elsevier Ltd. All rights reserved.


39. Suzuki W. et al. Formation and Isolation of a Four-Electron-Reduced Porphyrin Derivative by Reduction of a Stable 20 pi Isophlorin // Angew. Chem.-Int. Edit. 2018. Vol. 57, № 7. P. 1973–1977.

The two-electron reduction of a diprotonated dodecaphenylporphyrin derivative by Na2S2O4 gave a corresponding isophlorin (Iph) selectively. Formation of Iph was confirmed by spectroscopic measurements and the isolation of tetramethylated Iph. Further reduction of Iph proceeded to form an unprecedented four-electron-reduced porphyrin (IphH(2)), which was fully characterized by spectroscopic and X-ray crystallographic analysis. IphH(2), with a unique conformation, could be oxidized to reproduce the starting porphyrin, resulting in a proton-coupled four-electron reversible redox system.


40. Synthesis and Structural Characterization of Butadienylcalcium-based Heavy Grignard Reagents and a Ca-4[O] Inverse Crown Ether Complex

The structure elucidation of heavy Grignard reagents (RAeX, Ae = Ca, Sr, and Ba, X = halides) has been greatly strived after, mainly because of their inaccessibility and remarkable instability. The synthesis of a series of butadienyl-calcium compounds is presented, including 1-calcio-4-lithio1,3-butadiene, 1,4-dicalcio-1,3-butadiene, and a Ca-4[O] inverse crown ether complex, via the reaction between 1,4-dilithio-1,3-butadienes and calcium iodide in THF. Single-crystal X-ray analysis of these unprecedented heavy Grignard reagents revealed unique structural characteristics and bonding modes. Preliminary reaction chemistry was investigated. This study provides a novel class of alkenyl heavy Grignard reagents and a useful synthetic strategy for otherwise unavailable reactive organometallic compounds.


41. Tepper R. et al. Halogen-bond-based cooperative ion-pair recognition by a crown-ether-embedded 5-iodo-1,2,3-triazole // Chem. Commun. 2017. Vol. 53, № 14. P. 2260–2263.

A crown-ether containing the iodo-triazole moiety for simultaneous cation-anion binding through Lewis-basic nitrogen atoms and C-I center dot center dot center dot I halogen-bond-donating iodine atoms was prepared. The complexation of the heteroditopic receptor was illustrated by X-ray and DFT analysis. The cooperative effect boosting the anion affinity was quantified by H-1/C-13 NMR titration experiments.


42. Thomas K.E. et al. Stabilization and Structure of the cis Tautomer of a Free-Base Porphyrin // Angew. Chem.-Int. Edit. 2017. Vol. 56, № 34. P. 10088–10092.

Single-crystal X-ray analysis of the beta-heptakis(trifluoromethyl)-meso-tetrakis(p-fluorophenyl) porphyrin, H-2[(CF3)(7)TpFPP], has revealed the first example of a stable cis tautomer of a free-base porphyrin, the long-postulated intermediate of porphyrin tautomerism. The stability of the unique molecule appears to reflect a dual origin: a strongly saddled porphyrin skeleton, which alleviates electrostatic repulsion between the two NH protons, and two polarization-enhanced, transannular N-H center dot center dot center dot O-H center dot center dot center dot N hydrogen bond chains, each involving a molecule of water. DFT calculations suggest that the observed tautomer has a lower energy than the alternative, doubly hydrated trans tautomer by some 8.3 kcalmol(-1). A fascinating prospect thus exists that H-2[(CF3)(7)TpFPP]center dot 2H(2)O and cognate structures may act as supramolecular synthons, which, given their chirality, may even be amenable to resolution into optically pure enantiomers.


43. Uhl W., Stefaniak C., Layh M. Ga-Ga Bonds as Key Building Blocks for the Formation of Supramolecular Entities - Unusual Macrocyclic Tetra- and Octagallium Compounds // Eur. J. Inorg. Chem. 2017. № 15. P. 2270–2278.

Treatment of the digallium compound R2Ga-GaR2 (1) [R = CH(SiMe3)(2)] with the dicarboxylic acids 1,2- and 1,4-(HO2CCH2O)(2)C6H4 afforded, by the release of H2C(SiMe3)(2), macrocyclic compounds 2a and 2c, in which two organic spacer ligands connect two metal-metal bonds. Two CO2 groups bridge each Ga-Ga bond, and different structures resulted with a parallel or perpendicular arrangement of the bridging ligands. The resorcinol derivative 1,3-(HO2CCH2O)(2)C6H4 yielded the unique compound 2b, in which four Ga-Ga bonds are bridged by four spacer ligands. The organic groups form loops, which are alternately arranged above and below the molecular plane with four saddle points and a structure approaching (4) over bar symmetry. The 1,2-and 1,4-diacids afforded tetrakis(digallium) compounds 3a and 3c in the presence of water. In both cases carboxylate groups and hydroxido ligands bridge two Ga atoms of two different Ga-Ga bonds. The spacer ligands connect two of these fragments and adopt parallel orientations to form molecular boxes. Again, the 1,3-diacid afforded a unique structural motif in which a Ga4O6 skeleton (two Ga-Ga bonds) is bridged by a single organic spacer, reminiscent of the handle of a basket.


44. Wadhavane P.D. et al. Coordination behaviour of new open chain and macrocyclic peptidomimetic compounds with copper(II) // RSC Adv. 2015. Vol. 5, № 89. P. 72579–72589.

Two valine-derived bis(amino amides) ligands have been prepared and fully characterized. Both compounds contain additional functionalities that implement their basicity and their water solubility. Besides, compound 1 is an open chain ligand, while 2 is a macrocycle. Their protonation constants as well as their stability constants for the formation of the corresponding Cu2+ complexes have been determined potentiometrically. Important differences are associated to the macrocyclic effect and to the additional functionalities in the spacer. The presence of an additional amine group and/or the inclusion of a carboxylic side chain in this spacer increase the stabilities of the Cu2+ complexes, suggesting its participation in the interaction with the metal. Thus, 2 is the first pseudopeptidic cyclophane of this family displaying the ability to form highly stable metal complexes in water. UV-Vis and ESI-MS were used for analyzing the complex species detected in the speciation diagram.


45. Wang Y.-C. et al. Metal ion-modulated self-assembly of pseudo-suit[3] anes using crown ether-based terpyridine metalloprisms // Chem. Commun. 2016. Vol. 52, № 85. P. 12622–12625.

Two hexanuclear metalloprisms possessing three dibenzo[24] crown-8 units were generated in quantitative yields by complexation of the predesigned tetratopic 2,2':6',2 '' -terpyridine ligand (T) with Cd-II and Zn-II ions, respectively. The prismatic hosts were subsequently self-assembled with the trifunctional guest molecule (TriG) containing dibenzylammonium ions to afford the corresponding metallo-supramolecular pseudo-suit[3] anes. It was serendipitously found that the host-guest inclusion rates could be modulated by the subtle dynamic difference in metal-ligand frameworks, finally leading to a selective encapsulation event in the presence of both metallo-suits.


46. Wood D.M. et al. Guest-Induced Transformation of a Porphyrin-Edged (Fe4L6)-L-II Capsule into a (CuFe2L4)-Fe-I-L-II Fullerene Receptor // Angew. Chem.-Int. Edit. 2015. Vol. 54, № 13. P. 3988–3992.

The combination of a bent diamino(nickel(II) porphyrin) with 2-formylpyridine and Fe-II yielded an (Fe4L6)-L-II cage. Upon treatment with the fullerenes C-60 or C-70, this cage was found to transform into a new host-guest complex incorporating three Fe-II centers and four porphyrin ligands, in an arrangement that is hypothesized to maximize pi interactions between the porphyrin units of the host and the fullerene guest bound within its central cavity. The new complex shows coordinative unsaturation at one of the FeII centers as the result of the incommensurate metal-to-ligand ratio, which enabled the preparation of a heterometallic cone-shaped (CuFe2L4)-Fe-I-L-II adduct of C-60 or C-70.


47. Wu X.-W. et al. Synthesis and characterization of two novel bimetallic macrocyclic complexes generated from 1,2,4-triazole-containing semi-rigid ligands and M(NO3)(2) units (M = Ni and Zn) // Acta Crystallogr. Sect. C-Struct. Chem. 2016. Vol. 72. P. 285–+.

Bimetallic macrocyclic complexes have attracted the attention of chemists and various organic ligands have been used as molecular building blocks, but supramolecular complexes based on semi-rigid organic ligands containing 1,2,4triazole have remained rare until recently. It is easier to obtain novel topologies by making use of asymmetric semi-rigid ligands in the self-assembly process than by making use of rigid ligands. A new semi-rigid ligand, 3-[(pyridin-4-ylmethyl)sulfanyl]- 5-(quinolin-2-yl)-4H-1,2,4-triazol-4-amine (L), has been synthesized and used to generate two novel bimetallic macrocycle complexes, namely bis{mu 3-[(pyridin-4-ylmethyl) sulfanyl]-5-(quinolin-2-yl)-4H-1,2,4-triazol-4-amine} bis[( methanol-kappa O)(nitrato-kappa(2) O, O') nickel(II)] dinitrate, [Ni-2(NO3)(2)(C17H14N6S)(2)(CH3OH)(2)](NO3)(2), (I), and bis{mu-3-[(pyridin-4-ylmethyl) sulfanyl]-5-(quinolin2-yl)-4H-1,2,4-triazol-4-amine}bis[(methanol-mu O)(nitrato-kappa(2) O, O') zinc(II)] dinitrate, [Zn-2(NO3)(2)(C17H14N6S)(2)(CH3OH)(2)](NO3)(2), (II), by solution reactions with the inorganic salts M(NO3)(2) (M = Ni and Zn, respectively) in mixed solvents. In (I), two Ni II cations with the same coordination environment are linked by L ligands through Ni-N bonds to form a bimetallic ring. Compound (I) is extended into a two-dimensional network in the crystallographic ac plane via N-H center dot center dot center dot O, O-H center dot center dot center dot N and O-H center dot center dot center dot O hydrogen bonds, and neighbouring two-dimensional planes are parallel and form a three-dimensional structure via pi-pi stacking. Compound (II) contains two bimetallic rings with the same coordination environment of the Zn-II cations. The Zn-II cations are bridged by L ligands through Zn-N bonds to form the bimetallic rings. One type of bimetallic ring constructs a one-dimensional nanotube via O-H center dot center dot center dot O and NH center dot center dot center dot O hydrogen bonds along the crystallographic a direction, and the other constructs zero-dimensional molecular cages via O-H center dot center dot center dot O and N-H center dot center dot center dot O hydrogen bonds. They are interlinked into a two-dimensional network in the ac plane through extensive N-H center dot center dot center dot O hydrogen bonds, and a three-dimensional supramolecular architecture is formed via pi-pi interactions between the centroids of the benzene rings of the quinoline ring systems.


48. Xiong J. et al. Iso-Selective Ring-Opening Polymerization of rac-Lactide Catalyzed by Crown Ether Complexes of Sodium and Potassium Naphthalenolates // Inorg. Chem. 2015. Vol. 54, № 4. P. 1737–1743.

Two crown ether complexes of sodium and potassium naphthalenolates were synthesized and entirely characterized. The two complexes can iso-selectively catalyze the ring-opening polymerization (ROP) of rac-lactide at room temperature and afford polylactides with desired molecular weights and narrow PDIs; the best isotacticity (P-m) achieved was 0.73.


49. Yang C. et al. Formation of a Fluorous/Organic Biphasic Supramolecular Octopus Assembly for Enhanced Porphyrin Phosphorescence in Air // Angew. Chem.-Int. Edit. 2015. Vol. 54, № 16. P. 4842–4846.

The trinuclear triangle-shaped system [tris{3,5-bis(heptafluoropropyl)-1,2,4-triazolatosilver(I)}] (1) and the multi-armed square-shaped metalloporphyrin PtOEP or the free porphyrin base H2OEP serve as excellent octopus hosts (OEP=2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphine). Coupling of the fluorous/organic molecular octopi 1 and H2OEP or PtOEP by strong quadrupole-quadrupole and metal- interactions affords the supramolecular assemblies [1PtOEP] or [1H(2)OEP] (2a), which feature nanoscopic cavities surrounding the upper triangular and lower square cores. The fluorous/organic biphasic configuration of [1PtOEP] leads to an increase in the phosphorescence of PtOEP under ambient conditions. Guest molecules can be included in the biphasic double-octopus assembly in three different site-selective modes.


50. Yao Y. et al. Crystal structure of meso-substituted pyrazolyl porphyrin complexes and their highly active catalyst for oxidation of alkylbenzenes // Appl. Organomet. Chem. 2018. Vol. 32, № 3. P. e4184.

During the past few years, a great deal of effort has been devoted to the anchoring of catalytic oxidation. In this work, three new catalysts CuPp, MnPp and ZnPp by solvothermal methods with 5, 10, 15, 20-tetrakis(4-N-pyrazolyl)-phenyl porphyrin (H(2)Pp) and the corresponding metal salts have been synthesized and structurally characterized. The single crystal structures determined by X-ray diffraction show the bond distances of M-N in porphyrin cores determined the conformation of porphyrin rings. We explored the catalytic activity of CoPp, CuPp, MnPp and ZnPp for oxidation of alkylbenzenes. The experimental results display these products exhibit high catalytic activities and selectivities for oxidation of ethylbenzene to acetophenone, and can be reused by filtration without appreciable decrease in catalytic activity and selectivity.


51. Yu S. et al. Responsive Polypeptide-DNA Hydrogel Crosslinked by G-quadruplex // Acta Chim. Sin. 2015. Vol. 73, № 8. P. 815–818.

In the past thirty years, DNA molecule has received considerable attention as a promising building material due to its precise base-paring recognition, the programmable sequences, the predictable secondary structures, etc. Based on DNA self-assembly technique, DNA supramolecular hydrogels can be fabricated which are crosslinked networks swollen in an aqueous phase by the supramolecular interaction and also have widely applications in the biomedical field. In this paper, a new type of DNA-based supramolecular hydrogel was prepared by simply mixing two components: Polypeptide-DNA and G-quadruplex. We have successfully synthesized single-stranded DNA (ssDNA) grafted polypeptide via the copper-catalyzed click reaction. By introducing the intermolecular G-quadruplex structure, which is rich in guanine and is capable of forming a four-stranded structure in the presence of potassium, the hydrogel can be formed by DNA hybridization in a fast and in-situ manner and also obtain thermal and ionic responsive gel-sol transition, respectively. In this experiment, we firstly used polyacrylamide gel electrophoresis (PAGE), circular dichroism spectra (CD), UV-Vis spectroscopy to demonstrate the G-quadruplex structure formation, and the assembling process was efficient which are formed the parallel structure and the melting temperature (T-m) was about 43 degrees C. Then by the rheological tests, the shear-storage modulus (G') was obviously higher (up to 2.4 kPa) than the shear-loss modulus (G '') over the entire time range, and a minimum concentration of 0.5 wt% polypeptide-DNA was required to form a gel-like state, and the mechanical strength of the DNA hydrogels increased with increasing concentration of the DNA building blocks. What's more, the hydrogels can switch between the gel and the sol state when changing the temperature from 25 to 50 degrees C many times, indicating that the DNA hydrogels respond to thermal in a reversible way. At last, by using the properties of crown ether complexing potassium ion, the DNA hydrogel can obtain the ion responsiveness properties. Due to its designable responsiveness and good biocompatibility, this supramolecular hydrogel would have great potential applications in tissue engineering and 3D bioprinting field.


52. Zhang W. et al. Preparation and Characterization of Organic-norganic Hybrid Macrocyclic Compounds: Cyclic Ladder-like Polyphenylsilsesquioxanes // Inorg. Chem. 2018. Vol. 57, № 7. P. 3883–3892.

Organic-inorganic hybrid macrocyclic compounds, cyclic polyphenylsilsesquioxanes (cyc-PSQs), have been synthesized through hydrolysis and condensation reactions of phenyltrichlorosilane. Structural characterization has revealed that cyc-PSQs consist of a closed-ring double-chain siloxane inorganic backbone bearing organic phenyl groups. The cyc-PSQ molecules have been simulated and structurally optimized using the Forcite tool as implemented in Materials Studio. Structurally optimized cyc-PSQs are highly symmetrical and regular with high stereoregularity, consistent with the dimensions of their experimentally derived structures. Thermogravimetric analysis showed that these macrocyclic compounds have excellent thermal stability. In addition to these perfectly structured compounds, macrocyclic compounds with the same ring ladder structure but bearing an additional Si-OH group, cyc-PSQs-OH, have also been synthesized. A possible mechanism for the formation of the closed-ring molecular structures of cyc-PSQs and cyc-PSQs-OH is proposed.


53. Zheng J.-J. et al. Magnetic and electronic properties of porphyrin-based molecular nanowires // AIP Adv. 2016. Vol. 6, № 1. P. 015216.

Using spin-polarized density functional theory calculations, we performed theoretical investigations on the electronic and magnetic properties of transition metal embedded porphyrin-based nanowires (TM-PNWs, TM = Cr, Mn, Co, Ni, Cu, and Zn). Our results indicate that Ni-PNW and Zn-PNW are nonmagnetic while the rest species are magnetic, and the magnetic moments in TM-PNWs and their corresponding isolated monomer structures are found to be the same. In addition, the spin coupling in the magnetic nanowires can be ignored leading to their degenerate AFM and FM states. These results can be ascribed to the weak intermetallic interactions because of the relatively large distances between neighbor TM atoms. Among all TM-PNW structures considered here, only Mn-PNW shows a half-metallic property while the others are predicted to be semiconducting. The present work paves a new way of obtaining ferromagnetic porphyrin-based nanowires with TM atoms distributed separately and orderly, which are expected to be good candidates for catalysts, energy storage and molecular spintronics. (C) 2016 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution 3.0 Unported License.


54. Zhong D.-C., Lu T.-B. Molecular recognition and activation by polyaza macrocyclic compounds based on host-guest interactions // Chem. Commun. 2016. Vol. 52, № 68. P. 10322–10337.

The design and syntheses of supramolecular hosts for the recognition and activation of molecules and anions are one of the most active research fields in supramolecular chemistry, in which polyaza macrocyclic ligands and their complexes have drawn particular attention due to their strong host-guest interactions. This review mainly focuses on the recent progress in the recognition of molecules and anions by polyaza macrocyclic compounds including polyaza macrocycles, polyaza macrobicycles and polyaza macrotricycles, as well as the activation of molecules by polyaza macrocyclic ligands and their metal complexes.


55. Zhou W., Leznoff D.B. Phthalocyanine as a redox-active platform for organometallic chemistry // Chem. Commun. 2018. Vol. 54, № 15. P. 1829–1832.

A systematic approach to the synthesis of sigma-organometallophthalo-cyanines is described. Structurally characterized sigma-organoPcM complexes are presented, including the first PcCr-aryl, PcCr-alkynyl, and PcCr-Wittig complexes - representing the first examples of these classes of complexes for any metallophthalocyanine -and the first PcCr-alkyl complexes, which span three chromium and two Pc-ring oxidation states. This represents a rational marriage of the broad organometallic and phthalocyanine fields, opening the door for the exploration of this classical, stable, redox-active macrocycle as an ancillary ligand in metal-carbon chemistry.


56. 006651

Рассмотрены основные подходы к синтезу сорбентов на основе краун-эфиров - иммобилизация с ковалентным связыванием и без него. Приведены примеры получения сорбентов с использованием анодного окисления, химического модифицирования полимеров, реакций поликонденсации, химического модифицирования неорганических носителей, радиационно-химического синтеза для ковалентного связывания фрагментов краун-эфиров. Представлены методы иммобилизации краун-эфиров без ковалентного связывания: получение носителя в присутствии краун-эфира, пропитка готового носителя раствором краун-эфира, использование измельченного краун-эфира в качестве сорбента. Показаны области применения сорбентов для селективного извлечения стронция из растворов радиоактивных отходов и отработанного ядерного топлива, для радиохимического анализа (определения содержания стронция в воде, почве и биологических материалах), а также для разделения изотопов стронция и иттрия. Библиография - 114 ссылок.


57. 001713

При взаимодействии аминоимино-2-фенилиндандиона с бифенил-4,4''-диамином, 4,4''-cульфандиилдианилином и 4,4''-оксидианилином синтезированы линейные продукты конденсации и макроциклические соединения симметричного строения. Полученные соединения охарактеризованы данными ИК, УФ и ЯМР 1Н спектроскопии.


58. 001709

"Взаимодействием диимина 2-метилиндандиона с производными диаминобифенила (3,3''дихлор-, 3,3''-диметокси-, 2,2''-дисульфо-) синтезированы линейные продукты конденсации 2:1 и макроциклические соединения симметричного строения. Полученные соединения охарактеризованы данными ИК, УФ и ЯМР спектроскопии.


59. 001639
Вершинина И.А., Горнухина О.В., Голубчиков О.А. ИММОБИЛИЗАЦИЯ 5,10,15,20-ТЕТРАКИС(4'-КАРБОКСИЛФЕНИЛ)ПОРФИРИНА НА ПОВЕРХНОСТЬ МОДИФИЦИРОВАННОЙ ПОЛИПРОПИЛЕНОВОЙ ПЛЕНКИ // Российский химический журнал. 2014. Т. LVIII. № 3-4. С. 86-90.

"The immobilization of 5,10,15,20-tetrakis(4'-carboxy-phenyl)porphyrin on the surface modified polypropylene films was investigated. To activate the surface of the polypropylene the method of structural-chemical modification of the acrylamide and polyvinyl alcohol developed, which can increase the number immobilizing porphyrin 15-20 times. Modified materials possess of antimicrobial activity.


60. 002574
Вершинина И.А., Горнухина О.В., Кувшинова Е.М., Голубчиков О.А. ПОЛУЧЕНИЕ И СВОЙСТВА КОМБИНИРОВАННЫХ ПОЛИМЕРНЫХ МАТЕРИАЛОВ НА ОСНОВЕ 3,7,13,17-ТЕТРАМЕТИЛ-2,8,12,18-ТЕТРАЭТИЛ-5,15-БИС(4?-НИТРОФЕНИЛ)-ПОРФИРИНА И ЕГО МЕДНОГО КОМПЛЕКСА // Известия высших учебных заведений. Серия: Химия и химическая технология. 2016. Т. 59. № 11. С. 84-91.

Получены комбинированные материалы на основе химически активированных полимеров, 3,7,13,17-тетраметил-2,8,12,18-тетраэтил-5,15-бис(4?-нитрофенил)порфи-рина и его медного комплекса. Методами электронной, ИК спектрофотометрии и атомно-силовой микроскопии исследованы поверхностные свойства модифицированных материалов и определена их антибактериальная активность по отношению к грамотрицательным и грамположительным микроорганизмам.


61. 001889
Волошина Н.С., Камалов Г.Л. КРАУН-ЭФИРЫ, ИММОБИЛИЗОВАННЫЕ НА ПОВЕРХНОСТИ ПОЛИМЕРНЫХ МАТЕРИАЛОВ И КРЕМНЕЗЕМОВ // Физикохимия поверхности и защита материалов. 2014. Т. 50. № 5. С. 483.

Рассмотрены способы получения полимеров и сополимеров, содержащих фрагменты краун-эфиров (КЭ) и их производных, а также методы ковалентной и адсорбционной иммобилизации (закрепления) КЭ на поверхности различных кремнеземов ? силикагелей, аэросилов, силохромов и др. Продемонстрирована эффективность и перспективность полученных материалов в качестве катализаторов, специфических сорбентов, аналитических реагентов, экстрагентов, стационарных фаз и т.п. Обсуждаются особенности и возможные механизмы взаимодействия КЭ с поверхностными группами соответствующих носителей.


62. 001889
Волошина Н.С., Огниченко Л.Н., Кузьмин В.Е., Плужник-Гладырь С.М., Камалов Г.Л. СТРУКТУРНЫЕ ФАКТОРЫ ВЗАИМОДЕЙСТВИЯ КРАУН-ЭФИРОВ С ПОВЕРХНОСТЬЮ АЭРОСИЛА // Физикохимия поверхности и защита материалов. 2015. Т. 51. № 1. С. 61.

Предпринята попытка рассмотреть влияние строения и состава бензо-, дибензо- и “алифатических” краун-эфиров (более 40 соединений) на особенности их взаимодействия с поверхностными группами аэросила А-300, сопоставив коэффициенты Генри (KH) и константы Ленгмюра (KL), а также проанализировав методом QSPR (Quantitative structure?property relationships) основные факторы и фрагменты структуры, способствующие либо препятствующие образованию соответствующих “поверхностных соединений”.


63. 005659
Глухова О.Е., Колесникова А.С., Мельников Д.А., Салий И.Н., Слепченков М.М. ПЕРСПЕКТИВЫ ИСПОЛЬЗОВАНИЯ КРАУН-ЭФИРОВ ДЛЯ СОЗДАНИЯ НА ИХ ОСНОВЕ МИНИАТЮРНЫХ ИЗЛУЧАЮЩИХ СИСТЕМ // Радиотехника. 2015. № 10. С. 133-137.

Представлены результаты теоретического прогнозирования поведения иона щелочного металла внутри оболочки краун-эфирного соединения на примере молекулярной системы криптанда-222 с инкапсулированным ионом натрия. Изучены особенности атомного и электронного строения исследуемой молекулярной системы. Установлено наличие нерегулярных колебаний иона натрия внутри оболочки криптанда. Предложен механизм для стабилизации периода (частоты) колебаний с помощью внешнего электрического поля. Показано, что при определенной напряженности внешнего поля и температуре возможны колебания заряженного иона, сопровождающиеся излучением в терагерцевом диапазоне. На основе полученных результатов предложена модель излучающего элемента терагерцевой антенны.


64. 002574
Горнухина О.В., Вершинина И.А., Киселев А.Н., Кувшинова Е.М., Сырбу С.А., Голубчиков О.А. 5-[4?-(1,3-БЕНЗОТИАЗОЛ-2-ИЛ)ФЕНИЛ]-2,3,7,8,12,18-ГЕКСАМЕТИЛ-13,17-ДИ-Н-АМИЛ-ПОРФИРИН: СИНТЕЗ, КООРДИНАЦИОННЫЕ СВОЙСТВА И СОРБЦИЯ НА ПОЛИПРОПИЛЕНОВЫЕ МАТЕРИАЛЫ //Известия высших учебных заведений. Серия: Химия и химическая технология. 2018. Т. 61. № 1. С. 49-54.

Синтезирован 5-[4'-(1,3-бензотиазол-2-ил)фенил]-2,3,7,8,12,18-гексаметил-13,17-ди-н-амилпорфирин, исследованы его координационные свойства с ацетатами кобальта, меди и цинка в уксусной кислоте и пиридине. На основе полученных данных рассчитаны кинетические параметры реакции комплексообразования. Установлено, что в уксусной кислоте наблюдается увеличение скорости реакции комплексообразования в ряду: Co+2 <.Zn+2< Cu+2, при этом энергия активации уменьшается в полтора - два раза и существенно возрастает величина предэкспоненциального множителя. В пиридине наблюдается обратная зависимость. Медный и кобальтовый комплексы порфирина были использованы для поверхностной модификации химически активированных полипропиленовых материалов. Исходя из полученных электронных спектров, рассчитана эффективная поверхностная концентрация иммобилизованных порфириновых молекул. Показано, что наблюдается прямая зависимость количества привитых металлокомплексов от структуры поверхности полимера-носителя и условий иммобилизации макромолекул. Полученные модифицированные материалы протестированы на биоактивность с использованием водной суспензии агар-агара, инфицированного в отношении следующих культур: Staphylococcus aureus (грамм-положительная культура) и Escherichia coli (грамм-отрицательная культура) при микробной нагрузке 106 кл/мл. Результаты исследований показали, что полученные нами материалы обладают бактериостойкостью ко всем видам использованных патогенных микроорганизмов.


65. 001681
Демин С.В., Бочкарев А.В., Цивадзе А.Ю. РАСЧЕТ ИЗОТОПНЫХ ЭФФЕКТОВ ЛИТИЯ ?ЭКСТРАКЦИОННЫХ СИСТЕМАХ С?КРАУН-ЭФИРАМИ // Журнал неорганической химии. 2017. Т. 62. № 12. С. 1661-1665.



"С целью разработки новых нефототоксичных и чувствительных способов обнаружения новообразований про-веден синтез и исследованы основные спектрально-люминесцентные свойства наночастиц, содержащих иттер-биевый комплекс диметилового эфира протопорфирина IX (Yb-ПП) в полимерной матрице на основе лексана (ЛПМ). Наночастицы обладают увеличенным квантовым выходом и временем жизни люминесценции в ближней инфракрасной области (БИК) (~980 нм) и практическим отсутствием флуоресценции свободного основания пор-фирина в красной области спектра по сравнению с его комплексом в аналогичных концентрациях, что показыва-ет несомненную перспективность использования полученных наночастиц для диагностических целей.


67. 006793
Комолов А.С., Лазнева Э.Ф., Герасимова Н.Б., Зимина М.В., Si P., Панина Ю.А. ВОДОРАСТВОРИМЫЙ ФТАЛОЦИАНИН МЕДИ ДЛЯ ОПТИМИЗАЦИИ ГАЗОВЫХ СЕНСОРНЫХ ХАРАКТЕРИСТИК ДИОКСИДА ОЛОВА ПРИ АДСОРБЦИИ АММИАКА // Физика твердого тела. 2015. Т. 57. № 12. С. 2475-2478.

Приведены результаты исследований электропроводности тонких пленок наночастиц диоксида олова (SnO2), пленки молекул тетранатриевой соли 3,4'',4'''',4''''''-тетрасульфокислоты фталоцианина меди (CuPc-4SO3Na) и композитной пленки на основе смеси равных объемных частей этих двух материалов при адсорбции аммиака. Адсорбционные эксперименты выполнены в условиях вакуума при комнатной температуре при увеличении давления аммиака до 3·103 Pa от базового давления остаточных газов 5·10-1 Pa. В случае однокомпонентной пленки на основе наночастиц SnO2 увеличение электропроводности при этом достигало 100% и не являлось полностью обратимым при комнатной температуре после откачки газа. Для однокомпонентной пленки CuPc-4SO3Na и композитной пленки CuPc-4SO3Na/SnO2 наблюдалось увеличение их электропроводности в 400 и 150 раз соответственно. При откачке аммиака до базового давления электропроводность уменьшалась к исходным значениям в течение 1 s. Механизм влияния адсорбированных молекул аммиака на электропроводность исследованного композитного материала обсуждается с использованием модели формирования исследованного композитного образца, согласно которой органический компонент располагается в пустотах между наночастицами SnO2. Работа выполнена при поддержке научного гранта СПбГУ, РФФИ (грант N 14-03-00087а), National Natural Science Foundation of China (N 51301096) и Czech Science Foundation (проект N 14-36566G).



Устойчивость молекул [M(crown)A 2 ]/[M(crown)A]A, где M - двухзарядный катион металла, crown - некоторый краун-эфир, например, 18-краун-6, и A - подходящие лиганды/противоанионы, к взаимодействию с водой H 2 O, рассматривается, как функция двух аргументов - активационного барьера элементарной реакции вхождения молекулы H 2 O во внутреннюю сферу комплекса - первой стадии гидролиза, и прочности исходного молеку лярного комплекса с водой [M(crown)A 2 ]•H 2 O/[M(crown)A]A•H 2 O. Активационный барьер для вхождения воды во внутреннюю сферу комплекса зависит от соответствия ионного радиуса катиона M 2+ размеру полости макроцикла. На примере катионов M 2+ =Cu 2+ , Zn 2+ для ряда краун-эфиров 12-краун-4, 15-краун-5 и 18-краун-6 рассчитаны энергетические профили реакций вхождения H 2 O в комплексы [M(crown)Cl 2 ] / [M(crown)Cl]Cl. При несоответствии ионного радиуса металла радиусу полости краун-эфира вхождение воды и связывание её с центральным атомом происходит практически свободно, в то время как при согласованности геометриче ских параметров требуется преодолеть активационный барьер порядка ~15-20 ккал/моль. Устойчивость к гидролизу представляется зависящей от прочности молекулярных ассоциатов [M(crown)A 2 ]•H 2 O / [M(crown)A]A•H 2 O по сравнению с величиной активационного барьера вхождения воды во внутреннюю сферу комплек сов [M(crown)A 2 ] / [M(crown)A]A, и от энергетического эффекта при координации воды центральным атомом (после преодоления активационного барьера). Последний зависит от электронной природы центрального атома в комплексе, которую, по-видимому, можно охарактеризовать значениями электронного химического потенциала ? и жёсткости ? по Пирсону соединений M(crown)A 2 .


69. 001709

Вычислены внутренние константы связывания порфирина TMPyP4 с G-квадруплексом ДНК (ckit2), которые можно использовать в качестве стандарта для количественной оценки возможности участия этих структур в биохимических процессах. Вывод о существовании двух различных сайтов связывания между TMPyP4 и ckit2, сделанный ранее на основе ступенчатой модели комплексообразования, был пересмотрен с применением модели взаимного влияния (кооперативности) между лигандами, связанными с сайтами олигонуклеотида. Для проверки модели использован факторный анализ и метод анализа главных компонентов. Биомолекула ckit2 может рассматриваться как олигонуклеотид с эквивалентными взаимовлияющими сайтами связывания.


70. 008036

"Синтезированы и охарактеризованы 5-гидроксифенил-11,15,20-трифенилпорфирин и шесть соответствующих металлопорфиринов Mn, Fe, Co, Ni, Cu и Zn. Изучено их влияние на характеристики первичного элемента Li/SOCl2. Показано, что напряжение разряда под действием порфирина и металлопорфиринов Mn, Fe, Co и Ni (но не Cu и Zn) повышается на 20?120 мВ. Продолжительность разряда удлиняется на 26.7?157.6 с в присутствии порфирина и металлопорфиринов Mn, Ni и Zn. Максимальные начальные напряжения элемента в присутствии порфирина и всех шести металлопорфиринов также возрастают. Это показывает, что центральный ион металла оказывает влияние на процесс переноса заряда при восстановлении тионилхлорида.


71. 001709
Матвеева В.И., Князева И.Р., Сякаев В.В., Мамардашвили Н.Ж., Бурилов А.Р., Пудовик М.А. СИНТЕЗ НОВОГО ТИОФОСФОРИЛИРОВАННОГО МЕЗО-ЗАМЕЩЕННОГО ПОРФИРИНА // Журнал общей химии. 2015. Т. 85. № 11. С. 1932-1934.


72. 001713
Нуриев В.Н., Федоров О.В., Моисеева А.А., Фрейдзон А.Я., Курчавов Н.А., Ведерников А.И., Медведько А.В., Подъячева Е.С., Вацадзе С.З., Громов С.П. СИНТЕЗ, СТРУКТУРА, СПЕКТРАЛЬНЫЕ СВОЙСТВА И ЭЛЕКТРОХИМИЯ БИС(КРАУН-ЭФИР)СОДЕРЖАЩИХ 1,3-ДИСТИРИЛБЕНЗОЛОВ // Журнал органической химии. 2017. Т. 53. № 11. С. 1689-1699.

По реакции тетраэтил [1,3-фениленди(метилен)]бис(фосфоната) и формилпроизводных бензокраун-эфиров и о-диметоксибензола с высоким выходом получены бис(краун-эфир)содержащие и тетраметоксизамещенный 1,3-дистирилбензолы. С помощью спектроскопии ЯМР и квантово-химических расчетов найдено преобладание асимметричных син/анти,(син,анти),син/антиконформаций для 1,3-дистирилбензолов. 1,3-Дистирилбензолы поглощают в более коротковолновой области спектра и флуоресцируют слабее, нежели 1,4-дистирилбензолы. Затруднение процесса электрохимического восстановления 1,3-дистирилбензолов по сравнению с 1,4-дистирилбензолами обусловлено менее эффективной системой сопряжения в мета-производных


73. 003757
Нуруллина Н.М., Батыршин Н.Н., Харлампиди Х.Э., Анисимова В.И., Суворова И.А. КОМПЛЕКСЫ КРАУН-ЭФИРОВ С НЕПЕРЕХОДНЫМИ МЕТАЛЛАМИ КАК КАТАЛИЗАТОРЫ РАЗЛОЖЕНИЯ ГИДРОПЕРОКСИДОВ // Кинетика и катализ. 2016. Т. 57. № 4. С. 441-445.

Исследовано разложение гидропероксида трет-бутила в среде хлорбензола в присутствии комлексов краун-эфира дибензо-18-краун-6 с хлоридами кальция, стронция и бария. Установлено и кинетически доказано, что распаду гидропероксида трет-бутила предшествует образование промежуточного комплекса гидропероксид–катализатор. Определены кинетические и термодинамические параметры комплексообразования.


74. 001681

Изучена кинетика реакций образования и спектральные свойства донорно-акцепторных комплексов (5,10,15,20-тетра-(2-метоксифенил)порфинато)хлороиндия(III) с 2?-(пиридин-4-ил)-5?-(пиридин-2-ил)- 1?-(пиридин-2-ил)метилпирролидинил-[3?,4?:1,2][60]фуллереном. Реакция образования донорно-акцепторной диады [(Py3F)InTPP(2-OCH3)4]+ Cl- проходит в две стадии: как быстрая равновесная координация молекулы фуллеренового основания и медленное необратимое вытеснение аксиального хлорид-иона во вторую координационную сферу. Получены количественные характеристики равновесия и скорости. Продукты реакций идентифицированы методами ИК- и ЯМР 1Н спектроскопии. Определены важнейшие параметры электронно-оптических свойств и устойчивости порфирин-фуллереновых диад с внутри- и внешнесферным хлорид-ионом. Результаты актуальны при изучении фотофизики порфирин-фуллереновых диад и разработке фотопреобразователей на основе последних.


75. 002574
Плотникова А.О., Иванова Ю.Б., Мамардашвили Н.Ж. ИССЛЕДОВАНИЕ КОМПЛЕКСООБРАЗУЮЩИХ СВОЙСТВ 5,10,15,20-ТЕТРА(4-OH-ФЕНИЛ) ПОРФИРИНА В АЦЕТОНИТРИЛЕ И ДИМЕТИЛФОРМАМИДЕ // Известия высших учебных заведений. Серия: Химия и химическая технология. 2017. Т. 60. № 6. С. 65-71.

В настоящей работе методом спектрофотометрического титрования изучены реакции основного взаимодействия 5,10,15,20-тетра (4-ОН-фенил)порфирина в ацетонитриле с хлорной кислотой и проведена химическая кинетика лиганда с ацетатом цинка в диметилформамиде. Получены константы основной диссоциации протонированных кислот 5,10,15,20-тетра (4-ОН-фенил)порфирина и кинетические параметры реакции образования соответствующего цинкового комплекса. В работе проведен сравнительный анализ полученных собственных и литературных данных по основным и комплексообразующим свойствам 5,10,15,20-тетра(4-OH-фенил) порфирина и 5,10,15,20-тетрафенилпорфирина в ацетонитриле и диметилфорамиде в интервале 298-333 К, что позволило сделать ряд интересных выводов, касающихся стабилизации ионных форм лиганда в ацетонитриле и диметилформамиде и влияния растворителя на глубину протонирования лиганда и кинетическую скорость образования соответствующих цинковых комплексов. В работе показано, что стабилизация ионных форм лиганда при переходе от ацетонитрила к диметилформамиду снижает глубину протонирования лиганда, что отражается в уменьшении значений констант диссоциации катионных форм порфирина и кинетической скорости, и соответствующих энергетических затрат на реакцию образования ZnT(4-OH-Ph)P. В работе показано, что реакционная способность лиганда в диполярной апротонной среде может регулироваться изменением свойств этой среды, что позволяет прогнозировать процессы синтеза соединений с заданными свойствами.


76. 001766

Экспериментально исследованы электропроводность и адсорбционно-резистивный отклик на диоксид азота композитных пленок, содержащих наночастицы фталоцианина меди, диспергированные в матрицу полистирола. Полученные результаты проанализированы в рамках двухуровневой модели прыжковой проводимости. Выявлен вклад в проводимость собственных и примесных центров локализации, определены концентрация центров локализации во фталоцианине меди без примесей и радиусы локализации электронов в примесных и собственных состояниях.



Представлен анализ результатов теоретического моделирования сверхбыстрой кинетики фотоиндуцированного внутримолекулярного разделения зарядов из второго возбужденного синглетного состояния в диаде Zn-тетрафенилпорфирин-аминонафталиндиимида (Zn-TPP-ANDI) в растворе толуола. Расчеты выполнены в рамках многоканальной стохастической модели, включающей четыре электронных состояния (основное, первое и второе возбужденные синглетные состояния, состояние с разделенными зарядами), а также их колебательные подуровни, соответствующие возбуждению высокочастотных внутримолекулярных колебательных мод. Количественно воспроизведена двугорбая кинетическая кривая заселенности состояния с разделенными зарядами, наблюдаемая в эксперименте. Определены абсолютные значения выхода состояния с разделенными зарядами. Результаты моделирования показывают, что в реорганизацию низкочастотных мод большой вклад вносят внутримолекулярные моды. Выполнены квантово-химические расчеты с целью определения степеней свободы, связанных с внутримолекулярным медленным движением ядер большой амплитуды в диаде Zn-TPP-ANDI при переходе между основным состоянием и состоянием с разделенными зарядами.


78. Рочева Т.К., Буравлев Е.В., Мазалецкая Л.И., Шелудченко Н.И., Белых Д.В., Чукичева И.Ю., Кучин А.В. СИНТЕЗ И АНТИРАДИКАЛЬНАЯ АКТИВНОСТЬ МЕТАЛЛОКОМПЛЕКСОВ ТЕТРА(3,5-ДИИЗОБОРНИЛ-4-ГИДРОКСИФЕНИЛ)ПОРФИРИНА // акрогетероциклы. 2014. Т. 7. № 3. С. 262-266.

Исходя из тетра(3,5-диизоборнил-4-гидроксифенил)порфирина (1) синтезирован ряд комплексов с катионами переходных металлов (Zn 2+ , Cu 2+ , Co 2+ , Fe 3+ ). Оценка антирадикальной активности полученных соединений на основании кинетических характеристик реакции с ?-фенилэтилпероксильными радикалами показала, что антирадикальная активность исходного порфирина и его металлокомплексов обусловлена гидроксильными группами терпенофенольных заместителей. Среди изученных соединений максимальная антирадикальная активность, оцененная по величине стехиометрического коэффициента ингибирования, установлена для свободного основания 1, а для комплексов она уменьшается в ряду Zn-1 > Cu-1 > Co-1 > Fe(ОН)-1.


79. 006793
Свирский Г.И., Сергеева Н.Н., Красников С.А., Виноградов Н.А., Сергеева Ю.Н., Cafolla A.A., Преображенский А.Б., Виноградов А.С. ЭЛЕКТРОННАЯ СТРУКТУРА ПОРФИРИНА НИКЕЛЯ NIP: ИССЛЕДОВАНИЕ МЕТОДАМИ РЕНТГЕНОВСКОЙ ФОТОЭЛЕКТРОННОЙ И АБСОРБЦИОННОЙ СПЕКТРОСКОПИИ // Физика твердого тела. 2017. Т. 59. № 2. С. 357-366.

Энергетические распределения и свойства занятых и свободных электронных состояний для плоского комплекса порфирина никеля NiP исследованы методами рентгеновской фотоэмиссионной и абсорбционной спектроскопии. В результате анализа экспериментальных спектров валентной фотоэмиссии определен характер и энергетические положения верхних занятых электронных состояний: высшее занятое состояние сформировано в основном атомными состояниями порфинового лиганда, следующие два состояния связаны с 3d-состояниями атома никеля. Установлено, что низшее свободное состояние имеет специфический характер и описывается b1g-МО sigma-типа, которая формируется свободными Ni3dx2-y2-состояниями и занятыми 2p-состояниями неподеленных электронных пар атомов азота. Этот специфический характер низшего свободного состояния является следствием донорно-акцепторной химической связи в NiP.


80. 001639
Федорова О.В., Максимовских А.И., Корякова О.В., Русинова Г.Л., Мурашкевич А.Н., Рычков В.Н., Чарушина В.Н. КОМПОЗИТЫ КРАУН-ЭФИР-SIО2-TIО2 В ПРОЦЕССАХ СОРБЦИИ КАТИОНОВ МЕТАЛЛОВ ИЗ КИСЛЫХ ВОДНЫХ РАСТВОРОВ // Российский химический журнал. 2015. Т. LIX. № 5-6. С. 92-97.

"Путем добавления краун-эфира (дибензо-18-краун-6 или дибензо-21-краун-7) в процессе золь-гель синтеза оксидов SiО2-TiО2 получены композиты краун-эфир-SiО2-TiО2. Композиты исследованы в процессах сорбции катионов некоторых щелочных, щелочноземельных металлов и катионов РЗЭ в кислых средах. При переходе от краун-эфиров к их композитам на основе оксидов SiО2-TiО2, наблюдается увеличение эффективности и селективности сорбции катионов бария, а также катионов иттербия в присутствии катионов Sr(II), Ce(III), La(III), Nd(III). Методом ИК-спектроскопии показано, что адсорбция молекулы краун-эфира на поверхности оксида приводит к ее искажению, что может быть причиной изменения селективности в реакциях комплексообразования краун-эфира в композите краун-эфир-SiО2-TiО2.


81. 044297
Ходжаев Г.Х., Гасанова Н.Г. НЕКОТОРЫЕ АСПЕКТЫ СИНТЕЗА КРАУН-ЭФИРОВ // Нефтепереработка и нефтехимия. Научно-технические достижения и передовой опыт. 2017. № 12. С. 26-29.

В результате исследований разработана новая методология синтеза дибензо-, бензоаза-, спироаза-, бензтио- и других краун-эфиров. Получены высокие селективные выходы краун-эфиров за счёт изменения соотношения реагирующих компонентов и применения различных катализаторов (аммиака, эфирата трёхфтористого бора), а также условий реакции. Изучено межфазное дебромирование дибромалканов в присутствии синтезированных краун-эфиров.


82. Чижова Н.В., Звездина С.В., Кумеев Р.С., Мамардашвили Н.Ж. БРОМИРОВАНИЕ ?-ПОЛОЖЕНИЙ ТЕТРА(4-БРОМФЕНИЛ)-ПОРФИРИНА И ЕГО КОМПЛЕКСА C ZN(II) // Журнал органической химии. 2015. Т. 51. № 11. С. 1678-1680.

При взаимодействии 5,10,15,20-тетра(4-бромфенил)порфирина с N-бромсукцинимидом в смеси хлороформ-диметилформамид синтезирован 2-бром-5,10,15,20-тетра(4-бромфенил)порфирин. В аналогичных условиях бромирование 5,10,15,20-тетра(4-бромфенил)порфирината Zn(II) приводит к 2,3,12,13-тетрабром-5,10,15,20-тетра(4-бромфенил)порфиринату Zn(II). Бромированием ?-тетрабромзамещенного тетра(4-бромфенил)порфирината цинка N-бромсукцинимидом в смеси хлороформ-диметилформамид получен 2,3,7,8,12,13,17,18-октабром-5,10,15,20-тетра-(4-бромфенил)порфиринат Zn(II). Полученные соединения охарактеризованы методами электронной абсорбционной, ЯМР 1H спектроскопии и масс-спектрометрии.


83. 035033
Чуловская С.А., Кузьмин С.М., Шилов А.Н., Парфенюк В.И. ПОЛУЧЕНИЕ И СВОЙСТВА ПОЛУПРОВОДНИКОВЫХ ПЛЕНОК ПОЛИ-5,10,15,20-ТЕТРАКИС(4'-АМИНОФЕНИЛ)ПОРФИРИНА // Перспективные материалы. 2016. № 5. С. 33-40.

Получены пленки поли-5,10,15,20-тетракис(4'-аминофенил)порфирина (поли-H2T(p-NH2Ph)P) электрохимической полимеризацией при активации процесса синтезируемым электрохимически супероксид анион-радикалом из растворов диметилсульфоксида. Методом атомно-силовой микроскопии показано, что поверхность полученной пленки поли-H2T(p-NH2Ph)P имеет малую шероховатость и сформирована из однородных по химическому составу округлых глобул со средним размером около 40 нм. Согласно измерениям фотоэлектрического отклика обнаружено, что полученная поли-H2T(p-NH2Ph)P пленка является полупроводниковым материалом с проводимостью р-типа. Кинетика формирования пленки поли-H2T(p-NH2Ph)P на Pt электроде в диметилсульфоксиде охарактеризована методом спектроскопии электродного импеданса. В рамках модели Рэндлса-Эршлера изучены изменение емкости межфазной границы и фрактальной размерности поверхности пленки. Полученные зависимости указывают на стадийность формирования поли-H2T(p-NH2Ph)P пленки на Pt электроде.


84. Шабанов А.Л., Гахраманова З.О., Везирова Л.З., Гасанова У.А., Асадов М.М.СИНТЕЗ И СВОЙСТВА НОВЫХ КРАУН-СОЕДИНЕНИЙ, СОДЕРЖАЩИХ АМИННЫЕ И ГИДРОКСИЛЬНЫЕ ГРУППЫ В МАКРОЦИКЛИЧЕСКОМ КОЛЬЦЕ // Энциклопедия инженера-химика. 2014. № 10. С. 23-25.

Синтезированы краун-соединения с аминными и гидроксильной группами в макроциклическом кольце, имеющие перспективы применения в нанотехнологии. Предполагается, что наличие двух аминных групп и одной гидроксильной группы в макроциклическом кольце позволяет краун-эфиру (6) переходить из двухмерной (2D) структуры в трехмерную (3D). Строение полученных соединений установлено методами ИК-спектроскопического и хроматографического анализов и встречным синтезом.


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