The cation-induced dimerization of tetra-(15-crown-5)-substituted Al(III) phthalocyaninate with Na + , K + and Rb + salts in solution has been studied by 1 H NMR. It has been demonstrated that two types of supramolecular dimers coexist in solutions, which is consistent with the existence of both the monomeric and oxygen-bridged dimeric forms of the initial Al(III) complex. With the use of mass spectrometry (MALDI-TOF and HR-ESI), it has been shown that Al(III) monophthalocyaninate [(OH)AlR 4 Pc] forms supramolecular dimers {[M 4 (XAlR 4 Pc) 2 ] 4+ (X − ) 4 }, whereas Al(III) μ-oxodiphthalocyaninate [(AlR 4 Pc) 2 (μ-O)] forms oxygen-bridged supramolecular dimers {[M 4 (XAlR 4 Pc) 2 (μ-O)] 2+ (X − ) 2 }.

The formation of μ-oxo and μ-fluoro dimers based on aluminum tetra-15-crown-5-phthalocyanine Al[(15C5) 4 PcX], X = OH, OCH 3 ( I ) was studied by UV-Vis and 1 H NMR spectroscopy. It is established that the formation of μ-oxo dimer (μ-O)[(15C5) 4 PcAl] 2 in chloroform solution occurs upon titration of I with methanol, ethanol, and dimethylsulfoxide, as well as at the Al 2 O 3 -eluent interphase, upon an increase of the methanol concentration in chloroform and upon storage of I in the solid state. It is shown for the first time that the interaction of [(15C5) 4 PcAl(OH)] with tetrabutylammonium fluoride in chloroform results in the formation of stable μ-fluoro dimer of (μ-F)[(15C5) 4 PcAl] 2 + , structure of which identified based on UV-Vis, 1 H NMR, and MALDI-TOF mass spectral data. Conditions for preparation of complex [(15C5) 4 PcAlF 2 ] − in solutions are found, and the possibility of sequential transformations in the series of complexes [(15C5) 4 PcAl](OH) → [(15C5) 4 PcAlF 2 ] − → (μ-F)[(15C5) 4 Pcal] 2 + is shown.

Методом электронной спектроскопии поглощения и 1H ЯМР-спектроскопии изучены процессы формирования -оксо и -фторо-димеров на основе тетра-15-краун-5-фталоцианина алюминия Al[(15C5)4PcX], X = OH, OCH3 (I). Установлено, что образование -оксо-димера в растворе хлороформа происходит при титровании I метанолом, этанолом, диметилсуфоксидом, а также при хроматографической очистке на Al2O3 с увеличением полярности элюента и при хранении I в твердом виде. Впервые показано, что взаимодействие [(15C5)4PcAl(OH)] с фторидом тетрабутиламмония в хлороформе приводит к образованию устойчивого -фторо-димера состава идентифицированного по данным ЭСП, 1H ЯМР и MALDI-TOF масс-спектрометрии. Найдены условия получения комплекса состава [(15C5)4PcAlF2]- в растворах, а также показана возможность последовательных превращений в ряду комплексов состава [(15C5)4PcAl](OH) [(15C5)4PcAlF2]- .

Measurement of the photoelectric and photorefractive characteristics of 2,3,9,10,16,17,23,24-tetra(15-crown-5)phthalocyaninatoacetatoyttrium(III) [(15C5)4Pc]Y(OAc) has made it possible to reliably establish the features of decrease in the quantum yield of generation of charge carriers φ0 and photorefractive two-beam coupling gain Γ with an increase in the atomic weight of the central metal in a series of related gallium(III), yttrium(III), ruthenium(II), and indium (III) phthalocyaninates. These features can be due to an increase in the spin-orbit interaction constant with increasing atomic weight of the central metal, a change that leads to an increase in both the contribution of triplet excited associates to the formation of mobile charge carriers and the rate of the reverse reaction T 1 → S 0, which effectively inhibits the formation of charge carriers through the excited triplet state. The measurement of photoelectric and photorefractive characteristics at 1064 nm has shown that the quantum yield of electron-hole pairs in the composite polyvinylcarbazole/supramolecular assemblies of yttrium complex is φ0 = 0.6 and the two-beam coupling gain coefficient Γ is about 35 cm−1 at E 0 = 120 V/μm. The dielectric susceptibility measured by the z-scan technique in a solution of the yttrium complex in tetrachloroethane (1 mg in 1 mL) is χ(3) = 4.2 × 10−10 esu.

Photoelectric, nonlinear optical, and photorefractive properties of hybrid composite materials based on polyvinylcarbazole (PVK) and indium(III) 2,3,9,10,16,17,23,24-tetra(15-crown-5)phthalocyaninate [(15C5)4Pc]In(OH) are studied in detail. Field dependence of the quantum efficiency in a 7.8 μm-thick layer containing 5 at % [(15C5)4Pc]In(OH) is measured. The best approximation of the quantum efficiency with Onsager’s equation corresponds to a quantum yield of thermalized electron-hole pairs φ0 = 0.01 at initial separation r 0 = 9.8 Å. Z-scan measurements in a nanosecond range showed that the electric susceptibility of [(15C5)4Pc]In(OH) solution in tetrachloroethane (TCE) with a concentration of 7 × 10−4 mol/L is χ(3) = 1.34 × 10−9 esu. The maximum coupling gain coefficient found for the material composed of PVK and 5 wt % [(15C5)4Pc]In(OH) at an electric-field intensity of 200 V/μm is Γ = 80 cm−1, and the difference between the coupling gain and absorption coefficients is Γ − α = 70 cm−1. The dependence of the coupling gain coefficient on the intensity ratio of interfering beams 1 and 2 (β = I 1(0)/I 2(0)) in a composite containing 3 wt % [(15C5)4Pc]In(OH) is measured. An increase in β was attained by decreasing intensity of the signal beam I 2(0) at constant intensity of the pump beam I 1(0) = 0.15 W/cm2 and E 0 = 214 V/μm. Within the initial segment of the curve, the coupling gain coefficient increases from 30 to 60 cm−1; then, the coefficient drops almost to the initial value. The data obtained show that the composite materials studied can be used in practice for correcting faded images. The combined analysis of the results obtained and similar data for gallium and ruthenium tetra-15-crown-5-phthalocyaninate complexes revealed the regularities in the change of the quantum yield of thermalized electron-hole pairs and the photorefractive coupling gain coefficient in a series of complexing metals: gallium(III), ruthenium(II), and indium(III). An increase in the molecular weight of the central metal atom is found to result in a substantial decrease in Γ and φ0 due to the increase in the spin-orbit coupling constant.

X-ray diffraction analysis was used to establish the structure of aluminum(iii) alkoxide tetra-15-crown-5-phthalocyaninate complex.

Poly( N -vinylcarbazole) layers containing tetra-5-crown-5-gallium phthalocyaninate (R 4 Pc)Ga(OH) are shown to possess photoelectric and photorefractive sensitivity at a wavelength of 1064 nm. This effect is associated with the formation of supramolecular ensembles of (R 4 Pc)Ga(OH) molecules with electronic optical absorption in the near-IR range and nonlinear optical properties. For the composite containing 5 wt % (R 4 Pc)Ga(OH) supramolecular ensembles, the dependence of the quantum efficiency of mobile-charge photogeneration on electric field E 0 is well fit by the Onsager equation expanded to E 0 3 at a quantum yield of electron-hole pairs of φ 0 = 0.9 s with an initial separation radius of r 0 = 9.8 Å susceptibility χ (3) equal to 1.85 × 10 −10 esu is measured via the well-known method of electric-field-induced second-harmonic generation. Two-beam-coupling gain coefficient Γ is found to be 80 cm −1 at E 0 = 120 V/μm.

Впервые изучена способность трехпалубного комплекса гадолиния с тетра-15-краун-5-фталоцианином Gd2(R4Pc)3, (R–15-краун-5) (1) к формированию монослоев и пленок Лэнгмюра–Блоджетт (ПЛБ). Управление зарядовыми характеристиками молекул трехпалубного фталоцианината в монослое, их ориентацией и адгезией к водной субфазе осуществлялось путем изменения поверхностного давления, pH и состава субфазы (водные растворы, содержащие триэтилентетрамин (ТЭТА) и катионы металлов). Показано, что присутствие в субфазе Nа+ и протонированных аминогрупп ТЭТА приводит к росту предельной площади монослоя и значительному сокращению области существования жидкого состояния монослоя. Доказано, что наблюдаемые эффекты обусловлены конформационными и зарядовыми превращениями периферийных краун-эфиров, индуцируемыми их взаимодействием с катионами. Сопоставление дифференциальных спектров отражения монослоя комплекса на поверхности деионизированной воды с электронными спектрами поглощения трехслойной ПЛБ Gd2(R4Pc)3 и раствора комплекса в хлороформе указывает на то, что уже на стадии формирования монослоя на поверхности субфазы происходит частичное окисление комплекса и идет интенсивный процесс стэкинга. Электрохимические исследования 3-хслойных ПЛБ, проведенные методом циклической вольтамперометрии (ЦВА) на электродах из смешанных оксидов индия и олова (ITO-электродах), показали наличие в области потенциалов от –200 до 1100 мВ (относительно Ag+/AgCl) трех обратимых Red/Ox переходов. Причем все зафиксированные пики сохраняют и положение, и интенсивность при многократном циклировании. Измерения, проведенные методом поверхностного плазмонного резонанса при наложении внешнего потенциала, позволили выделить 3 стабильных редокс состояния исследуемой ПЛБ. Такое поведение демонстрирует возможность использования многоступенчатых редокс-преобразований в ПЛБ исследуемого комплекса для создания стабильных и воспроизводимых переключаемых оптоэлектронных систем.

Erbium mono-, bis-, and tris(phthalocyaninates) with tetra-15-crown-5-phthalocyanine (H 2 R 4 Pc) were synthesized and studied by spectroscopic methods. The complexes were obtained by reacting H 2 R 4 Pc with erbium salts in high-boiling solvents. To compare the efficiency of two approaches to the synthesis of double-decker lanthanide phthalocyaninates, bis(phthalocyaninate) [Er(R 4 Pc) 2 ] was also obtained by a template procedure from dicyanobenzo-15-crown-5. A combination of physicochemical methods (UV and IR spectroscopy, MALDI-TOF mass spectrometry, 1 H NMR) was used for identifying the compounds and proving their individuality and structure. The photoluminescence method demonstrated that solutions of erbium bis- and tris(phthalocyaninates) in CHCl 3 are nonfluorescent in the visible range of light whereas solutions of mono(phthalocyaninate) in CHCl 3 and DMSO exhibit fluorescence with maxima at 707 and 695 nm, respectively. The oxidation of erbium mono(phthalocyaninate) leads to fluorescence quenching.

The ability of the triple-decker gadolinium complex with tetra-15-crown-5-phthalocyanine Gd2(R4Pc)3, (R = 15-crown-5) (1) to form monolayers and Langmuir-Blodgett films (LBFs) was studied for the first time. The charge characteristics of molecules of a triple-decker phthalocyaninate in monolayer, as well as their orientation and adhesion to the water subphase, were controlled by changing the surface pressure, pH, and subphase composition (aqueous solutions containing triethylenetetramine (TETA) and metal cations). It was shown that the presence of Na+ and protonated TETA aminogroups in resulted in an increasing limiting monolayer area and significant decreasing of the monolayer liquid state region. It is proven that the observed effects are caused by the conformational and charge transitions of peripheral crown ethers induced by their interaction with cations. A comparison of the differential reflectance spectra of the complex monolayer on the deionized water surface with UV-Vis absorption spectra of three-layer Gd2(R4Pc)3 LBF and complex solution in chloroform shows that partial complex oxidation and intensive stacking formation occurs already at the stage of monolayer formation on the subphase surface. Electrochemical studies of three-layer LBFs performed at the indium-tin-oxide electrodes (ITO-electrodes) using cyclic voltammetry (CV) showed three reversible redox waves in the potential range −200 to +1100 mV (vs. Ag+/AgCl). All registered peaks remain the same position and intensity upon multiple cycling. plasmon resonance (SPR) measurements allow to register three stable redox states of studied LBF upon applying the external potential. Such behavior shows the possibility to use multistep redox transformations of studied complex LBF for developing of stable and reproducible switchable optoelectronic systems.

The cation-induced aggregation of sandwich crown-substituted complexes [Ln(R4Pc)2] (Ln = Lu (I) and Yb (II), R4Pc2− is the 4,5,4′,5′,4″,5″,4‴,5‴-tetrakis(1,4,7,10,13-pentaoxatridecamethylene)phthalocyaninate ion) and Ln2(R4Pc)3(Ln = Lu (III) and Yb (IV) in a CDCl3-DMSO-d 6 solution has been studied by 1H NMR. The data obtained are consistent with the conclusions concerning the composition of supramolecular aggregates drawn from spectrophotometric titration data. The molecules of double-decker complexes I and II form supramolecular oligomers, whereas triple-decker complexes III and IV form supramolecular dimers, which is presumably due to the stronger distortion of the planes of the outer decks of the triple-decker complexes as compared to their double-decker analogues.

The scandium(III) complexes with tetra(15-crown-5)phthalocyanine [Sc(R 4 Pc) 2 ] ·0 ( I ) and Sc(R 4 Pc) · OAc ( II ) have been synthesized by condensation of Sc 3+ with phthalocyanine H 2 R 4 Pc (4,5,4′,5′,4″,5″,4‴,5‴-tetrakis(1,4,7,10,13-pentaoxatridecamethylene)phthalocyanine). Compounds I and II have been characterized by spectral methods: electronic absorption spectroscopy, MALDI-TOF MS, IR spectroscopy, and 1 H NMR. The redox properties of I and the photoluminescent properties of II have been studied.

Синтезированы комплексы Sc(III) с тетра(15-краун-5)фталоцианином составов [Sc(R4Pc)2].0 (I) и Sc(R4Pc) · OAc (II) методом конденсации Sc3+ c фталоцианином, H2R4Pc (4, 5, 4, 5, 4, 5,4, 5 -тетракис(1, 4, 7, 10, 13 – пентаоксатридекаметилен)фталоцианин). Соединения I и II охарактеризованы спектральными методами: ЭСП, MALDI-TOF-MS, ИК, ЯМР1H. Изучены окислительно-восстановительные свойства [Sc(R4Pc)2].0, а также фотолюминесцентные свойства Sc(R4Pc) · OAc.

The products of 4′,5′-dibromobenzo-15-crown-5 ( I ) cyanation by the Rosenmund-Braun reaction are studied by the 1 H NMR and IR spectroscopy methods. X-ray diffraction analysis of two isolated products, i.e., di(4′,5′-dicyanobenzo-15-crown-5) 1.6 hydrate {(CN) 2 B15C5} 2 · 1.6H 2 O ( IIa ) and 4′,5′-dicyanobenzo-15-crown-5,4′-cyano-5′-cyano(bromo)benzo-15-crown-5 dihydrate (CN) 3.85 Br 0.15 (B15C5) 2 · 2H 2 O ( III ) is performed. Crystals IIa are monoclinic, a = 15.882(2) Å, b = 11.412(2) Å, c = 18.484(3) Å, β = 100.717(3)°, V = 3291.7(9) Å 3 , Z = 4, space group P 2 1 / c, R = 0.0746 for 4775 reflections with I > 2σ( I ). Crystals III are monoclinic, a = 15.956(3) Å, b = 11.425(2) Å, c = 18.865(4) Å, β = 99.32(3)°, V = 3394(1) Å 3 , Z = 4, space group P 2 1 / c, R = 0.0692 for 2070 reflections with I > 2σ( I ). Compounds IIa and III have similar structures with two crystallographically independent molecules in each ( A and B in IIa ; C and D in III ). Four of the five O atoms of a macrocycle in molecules A and C form hydrogen bonds with the water molecules. The latter molecules lie above and below the cycle plane at a distance of ∼2 Å from this plane. The A and C molecules have identical conformations ( TTG TTG TTG TTG TTC ) that differ from those of molecules B ( TTG TGG STT SSG TTC ) and D ( TTC TSG STT SSG TTC ).

Complexing properties of lanthanide ions with respect to crown-substituted phthalocyanine are analyzed. Complexes of lanthanides (La, Nd, Sm, Eu, Gd, Tb, Yb, Lu, Y) with tetra-15-crown-5-phthalocyanine are synthesized and their structures are studied by photoelectronic, IR, 1H NMR, and mass spectrometry methods.

The cation-induced supramolecular organization of sandwich crown-substituted rare-earth phthalocyaninates in organic solvents in the presence of alkali-metal thiocyanates has been studied by spectrophotometry. KSCN reacts with a triple-decker lutetium complex in CHCl3 to form the cofacial dimers 2Lu(2)(R4Pc)(3).4KSCN (R4Pc2- = 4,5,4',5',4", 5",4"', 5"'-tetrakis(1,4,7,10,13-pentaoxatridecamethylene)phthalocyaninate ion). The nitrogenous base 1,8-diazabicyclo[5.4.0]undec-7-ene can reduce monoradical rare-earth phthalocyaninate (Y3+ Gd3+, Yb3+, Lu3+). The interaction of alkali-metal (K+, Rb+, Cs+) thiocyanates with one-electron-reduced diphthalocyaninates forms contributes to their organization in polymeric cofacial aggregates with the composition { [Ln(R4Pc)(2)(-) . M+] . 3MSCN}(N).

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.