Synthesis of (trans-A2)BC-Type Porphyrins with Acceptor Diethoxyphosphoryl and Various Donor Groups and their Assembling in the Solid State and at Interfaces

International audienceA versatile synthetic approach to accessing unsymmetrically substituted (trans-A2)BC-type porphyrins bearing two heteroatoms at the macrocycle periphery is developed. For this purpose, experimental conditions for the substitution of the bromine atom in zinc 5-bromo-15-(diethoxyphosphoryl)-10,20-diphenylporphyin (2) by S-, O-and N-nucleophiles were explored. SNAr reactions afford AlkO-, ArO-and AlkS-substituted porphyrins in good to high yields. In contrast, SNAr reactions of 2 with N-nucleophiles lead to meso-amino-substituted porphyrins in preparative yields only with cyclic secondary amines. Primary amines, anilines and azacrowns may also react with bromide 2 but the palladium catalyst is needed to obtain the products in acceptable yields. The interest of the compounds under investigation for biomimetic assembly of tetrapyrroles was demonstrated by the studies of self-assembly of ditopic morpholinyl-substituted porphyrin 5a in the solid state. Moreover, we have prepared emissive porphyrin monolayers at the air/water interface and revealed that the porphyrin films were suitable for detection of zinc(II) ions in aqueous solutions

Nicotinamide complex of silver(III) with expanded coordination number

In strongly alkaline media ([OH-] ≥ 0.12 M), nicotinamide (nica) forms a complex with square-planar Ag(OH)4- [nica] ≥ 0.05 M. The complex decomposes in seconds to nicotinamide N-oxide. The correlation of maximum absorbance of the complex with concentrations of nicotinamide and hydroxide requires that the complex is either the five-coordinate Ag(OH)4(H-1nica)2- or the six-coordinate Ag(OH)5(nica)2-. Comparison with the reactions of Ag(OH)4- with nicotinate ion (nic-) and acetamide under similar conditions indicates that nicotinamide coordinates with Ag(OH)4- by the amido group rather than the nitrogen on the pyridine ring or the amido oxygen. Kinetics of the Ag(III)- nica redox reaction are consistent with direct reaction between nicotinamide and uncoordinated Ag(OH4)-. Oxidation takes place at the pyridine ring, yielding nicotinamide N-oxide. Silver(III) is reduced to monovalent silver

Electronic structure and NH-tautomerism of a novel metal-free phenanthroline-annelated phthalocyanine

A novel low-symmetry A3B-type phthalocyanine annelated with a pyrazino[2,3-f]phenanthroline ring system and substituted with six solubilizing diisopropylphenoxy-groups (1) was synthesized by metalfree DBU-promoted cross-condensation of diiminoisoindolines derived from 4,5- bis(diisopropylphenoxy)phthalonitrile and pyrazino[2,3-f][1,10]phenanthroline-2,3-dicarbonitrile. The use of these particular precursors affords A3B phthalocyanine in 15% yield, while cross-condensation of the corresponding dinitriles yields only trace amounts of the target compound. Comparative studies of the A3B-type phthalocyanine and its symmetrical octa(diisopropylphenoxy)-substituted counterpart 2 reveal striking differences in the Q band regions of their UVevisible absorption (UVeVis) spectra, which could be readily rationalized through a comparison with calculated TD-DFT spectra. Since 1 can have two NH-tautomers with equivalent and non-equivalent NH-groups, and DFT calculations predict that the former tautomer is only 2.3 kcal/mol more stable than the latter one, a comprehensive analysis of 13C NMR spectra was carried out through the application of 1 He13C HMBC and HSQC techniques. It demonstrated that only the tautomer with equivalent NH-groups is present in solution

Formation principles of layers from active carbon microparticles with grafted amine derivatives of PVC on substrate

Porous layers from activated carbon with macro-molecular cyclic amines based on PVC and modyfied by primary amines were synthesized and its properties were described. Layers were grafted to the surface of a PVC film, cotton medical gauze and asbestos fabric. The nature of benzyl alcohol solvatation and the mechanism of suspension formation within layers of macro-molecular cyclic amines were investigated by methods of IR-spectroscopy and luminescence spectroscopy and described. The structural features of grafted PVC was identified and the influence of the substrate nature on the structure was traced. Upon contact of particles with benzyl alcohol molecules from solvatocomplexes PVC-related aromatic groups replace benzyl alcohol in solvatocomplexes. This leads to non-covalent binding of groups on the surface of the particles. It was shown that sorption of organic molecules does not affect the number of structural types of oxoamines

MCD spectroscopy and TD-DFT calculations of magnesium tetra-(15-crown-5-oxanthreno)-phthalocyanine

An analysis of the MCD spectroscopy and TD-DFT calculations of magnesium tetra-(15-crown-5-oxanthreno)-phthalocyanine is reported. This study provides a reassessment of an earlier study on the nature of the bands in UV-visible absorption spectra of magnesium and zinc tetra-(15-crown-5-oxanthreno)-phthalocyanine that was based on an analysis of TD-DFT calculations for a series of model complexes with the B3LYP functional. A detailed analysis of MCD spectral data and TD-DFT calculations with the CAM-B3LYP functional for the complete Mg(II) complex provides an additional insight into the optical properties and electronic structures of tetra-(15-crown-5-oxanthreno)-phthalocyanines. Thus, the bands in the Q-band region are reassigned as being due exclusively to the Q transition of Gouterman’s 4-orbital model, since intense pseudo-A11 terms are observed in the MCD spectrum in a spectral region that had previously been assigned as charge transfer bands

Methodological Survey of Simplified TD-DFT Methods for Fast and Accurate Interpretation of UV−Vis−NIR Spectra of Phthalocyanines

A methodological survey of density functional theory (DFT) methods for the prediction of UV−visible (vis)−near-infrared (NIR) spectra of phthalocyanines is reported. Four methods, namely, full time-dependent (TD)-DFT and its Tamm−Dancoff approximation (TDA), together with their simplified modifications (sTD-DFT and sTDA, respectively), were tested by using the examples of unsubstituted and alkoxy-substituted metal-free ligands and zinc complexes. The theoretical results were compared with experimental data derived from UV−visible absorption and magnetic circular dichroism spectroscopy. Seven popular exchange-correlation functionals (BP86, B3LYP, TPSSh, M06, CAM-B3LYP, LC-BLYP, and ωB97X) were tested within these four approaches starting at a relatively modest level using 6-31G(d) basis sets and gas-phase BP86/def2-SVP optimized geometries. A gradual augmentation of the computational levels was used to identify the influence of starting geometry, solvation effects, and basis sets on the results of TD-DFT and sTD-DFT calculations. It was found that although these factors do influence the predicted energies of the vertical excitations, they do not affect the trends predicted in the spectral properties across series of structurally related substituted free bases and metallophthalocyanines. The best accuracy for the gas-phase vertical excitations was observed in the lower-energy Q-band region for calculations that made use of range-separated hybrids for both full and simplified TD-DFT approaches. The CAMB3LYP functional provided particularly accurate results in the context of the sTD-DFT approach. The description of the higherenergy B-band region is considerably less accurate, and this demonstrates the need for further advances in the accuracy of theoretical calculations. Together with a general increase in accuracy, the application of simplified TD-DFT methods affords a 2−3 orders of magnitude speedup of the calculations in comparison to the full TD-DFT approach. It is anticipated that this approach will be widely used on desktop computers during the interpretation of UV−vis−NIR spectra of phthalocyanines and related macrocycles in the years ahead

Photophysics and NLO properties of Ga (III) and In (III) phthalocyaninates bearing diethyleneglycol chains

This work reports on synthesis and characterizations of Ga(III) and In(III) complexes, formed by 2,3-bis[2′′-(2′′′′-hydroxyethoxy)ethoxy]-9,10,16,17,23,24-hexa-nn-butoxy phthalocyanine (1H2) coordinating acetatoindium(III) (1InOAc) and hydroxogallium(III) (1GaOH) Photophysical properties of hydroxogallium(III) phthalocyaninate 1GaOH and acetatoindium(III) phthalocyaninate 1InOAc were studied by UV-vis, fluorescence spectroscopy and time-resolved methods. The nonlinear absorption of the complexes was studied using the Z-scan technique at 532 nm and 10 ns pulse in DMSO and in thin films formed by composite with poly(bisphenol A carbonate) — PBC. The magnitude of absorption coefficients and other nonlinear optical parameters estimated in this work showed that complex 1InOAc exhibited the strongest nonlinear optical behavior in comparison with 1GaOH in solution and a reverse tendency when embedded in PBC thin films. DFT calculations were used to rationalize these results

Improvement of nonlinear optical properties of phthalocyanine bearing diethyleneglycole chains

This paper reports the successful synthesis of the low symmetry phthalocyanines: metal-free 2,3-bis[2′-(2′′-hydroxyethoxy)ethoxy]-9,10,16,17,23,24-hexa-nn-butoxyphthalocyanine 1H22 and its zinc complex 1Zn along with their nonlinear optical (NLO) behavior in solution and in thin films. 1H NMR investigations evidenced of higher dissymmetry of electronic density in 1H22 in comparison with 1Zn. This dissymmetry is responsible for unusually higher values of Im[χ(3)χ(3)]/αα, βeffβeff, and γγ for 1H22in contrast to 1Zn, where the notable effect of heavy-metal enhancement of ISC was expected. Both compounds showed Im[χ(3)χ(3)]/αα values of the order of 10−11−11 in chloroform which are higher in comparison to the symmetrical octabutoxyphthalocyanine H2[(BuO)8Pc]. NLO properties of 1H22 were improved via its incorporation into polycarbonate polymeric matrix together with CdSe@CdS-TOPO quantum dots. In such composite the value of Im[χ(3)χ(3)]/αα was almost three times higher in comparison with 1H22 solution in chloroform. The obtained composites are expected to be perspective components of optical materials, capable of protection against strong light irradiatio

Layers of active carbon with grafted sodium and potassium glycinate derivatives on the surface of PVC film

Porous layers from active carbon with macro-molecular cyclic amines with sodium or potassium acetate substituents were synthesized. Layers sewn to the surface of a film of PVC. It is shown that the graft zones around carbon particles consist of luminophore groupings in the form of conjugated rings, including radicals with substituted amino groups, conjugated carbon groups and oxygen atoms binding these groups. The electronic conductivity of the layers and their sorption capacity for the absorption of benzene vapor are measured. It is established that the conductivity of the layer is the higher, the smaller the PVC derivatives, the carbon particles are combined. The conductivity of the layers with potassium ions is greater than that of sodium ions. It is assumed that most of the vapors are concentrated in the pores in the carbon. The sorption capacity of layers with sodium ions is greater than that of potassium ions

ЭКСТРАКЦИОННО-ХРОМАТОГРАФИЧЕСКОЕ ОПРЕДЕЛЕНИЕ НЕПТУНИЯ И ПЛУТОНИЯ В РАФИНАТНЫХ РАСТВОРАХ ПЕРЕРАБОТКИ ОТРАБОТАННОГО ЯДЕРНОГО ТОПЛИВА С ИСПОЛЬЗОВАНИЕМ СОРБЕНТА, ИМПРЕГНИРОВАННОГО СМЕСЬЮ ФОСФОРИЛПОДАНДА КИСЛОТНОГО ТИПА И НИТРАТА МЕТИЛТРИОКТИЛАММОНИЯ

An extraction chromatographic separation of Np(IV) and Pu(IV) from the raffinate reprocessing solutions of spent nuclear fuel using polymer sorbent impregnated with the mixture of acid type phosphorylpodand 1,5-bis[2-(oxyethoxyphosphinyl)-4-(ethyl)phenoxy]-3-oxapentan and quaternary ammonium base methyltrioctylammonium nitrate was performed. The effect of nitric acid and ammonium oxalate concentrations on the sorption of neptunium, plutonium, uranium, thorium and zirconium was studied. The techniques for measuring the content of  Np(IV) and Pu(IV) in the processed products of spent nuclear fuel using high performance liquid chromatography with spectrophotometric detection were proposed. Limits of detection for neptunium and plutonium were 5·10‑5 g·dm‑3 and 1.3·10-5 g·dm‑3  respectively. The duration of the analysis considering two parallel determinations does not exceed 40 min.Key words: еxtraction chromatography, phosphorylpodand, methyltrioctylammonium nitrate (МТОАN), carrier, plutonium, neptunium(Russian)DOI: http://dx.doi.org/10.15826/analitika.2013.17.3.007E.V. Chukhlantseva1, A.N. Usolkin1, V.E. Baulin 2,3, O.V. Kovalenko2, L.K. Neudachina4, A.Yu. Tsivadze3  1Federal State Unitary Enterprise "Production Association Mayak", Ozyorsk, Russia2Russian academy of sciences A.N. Frumkin Institute of Physical chemistry and Electrochemistry RAS, Moscow, Russia3Russian academy of sciences Institute of Physiologically Active Compounds RAS, Chernogolovka, Russia4Ural Federal University named after the first President of Russia B.N. Yeltsin, Ekaterinburg, RussiaОсуществлено экстракционно-хроматографическое выделение Np(IV), Pu(IV) из рафинатных растворов переработки отработанного ядерного топлива (ОЯТ) полимерным сорбентом, импрегнированным смесью фосфорилподанда кислотного типа - 1,5-бис[2-(оксиэтоксифосфинил)-4-(этил)фенокси]-3-оксапентаном, с четвертичным аммониевым основанием нитратом метилтриоктиламмония. Изучено влияние концентрации азотной кислоты, оксалата аммония на сорбцию нептуния, плутония, урана, тория и циркония. Предложены методики измерений содержания Np(IV) и Pu(IV) в продуктах переработки ОЯТ в варианте высокоэффективной жидкостной хроматографии со спектрофотометрическим детектированием. Пределы обнаружения нептуния и плутония составили 5·10-5 г/дм3 и 1.3·10-5 г/дм3 соответственно. Продолжительность анализа с учетом выполнения двух параллельных определений – не более 40 мин. Ключевые слова: экстракционная хроматография, фосфорилподанд, метилтриоктиламмоний нитрат (МТОАН), носитель, плутоний, нептунийDOI: http://dx.doi.org/10.15826/analitika.2013.17.3.007 Литература1. Саввин С. Б. Органические реагенты группы арсеназо III. М.: Атомиздат, 1971. 350 с.2. Браун Т., Герсини Г. Экстракционная хроматография. М.: Мир, 1978. 628 с.3. Баулин В.Е. Фосфорилсодержащие поданды. Синтез, свойства и применение. Автореф. … д-ра хим. наук. М., 2012. 49 с.4. Экстракционно-хроматографическое выделение и разделение тория, урана, нептуния и плутония сорбентами, импрегнированными фосфорилподандом кислотного типа и его смесями с нитратом метилтриоктиламмония / Е.В. Чухланцева и [др.] // Аналитика и контроль. 2013. Т. 17, № 2. С. 219-227. 5. Экстракционно-хроматографическое отделение плутония от других веществ с применением альфа-детектора для измерения его концентрации в растворах / В.К. Марков и [др.] // Радиохимия. 1976. Т. 18, № 5. С. 751-765.6. МИ 2335-2003. Внутренний контроль качества результатов количественного химического анализа. ФГУП «УНИИМ», 2003. 7. Дерффель К. Статистика в аналитической химии. М.: Мир, 1994. 268 с.