ISSN 1070-3632, Russian Journal of General Chemistry, 2010, Vol. 80, No. 9, pp. 1864–1870. © Pleiades Publishing, Ltd., 2010. Original Russian Text © V.N. Myakov, M.A. Lopatin, T.I. Lopatina, V.I. Faerman, 2010, published in Zhurnal Obshchei Khimii, 2010, Vol. 80, No. 9, pp. 1547–1553.

Some Donor-Acceptor Complexes of Silicon Phthalocyanine Dianions V. N. Myakov, M. A. Lopatin, T. I. Lopatina, and V. I. Faerman Institute of Organometallic Chemistry, Russian Academy of Sciences, ul. Tropinina 49, Nizhnii Novgorod, 603950 Russia e-mail: [email protected] Received December 3, 2009

Abstract―Studying the reaction of PcSiX2 (X = Cl, OH) with KOH in DMSO we first discovered red D–A complexes [(Pc2–)·PcSiX2] and [(Pc2–)·O2] in which silicon phthalocyanine dianion Pc2– is a donor, and the parent phthalocyanine silicon or oxygen are acceptors of electron density. The complexes were characterized by electron absorption, NMR, and ESR spectra. In the reactions with Me3SiCl, H2O, or CH3COOH the complexes regenerate phthalocyanine and O2. In O2 atmosphere the [(Pc2–)·O2] complex gradually degrades affording a product of unknown nature.

DOI: 10.1134/S1070363210090252 Metal phthalocyanines (MPc) belong to a class of widely studied and used organic compounds. They are used both in the fundamental and applied research relating to catalysis, molecular electronics, nonlinear optics, photodynamic therapy of cancer, etc. [1, 2]. Such a variety of physical, chemical and catalytic properties of phthalocyanines is defined by unique electron system of their 18-π-electron aromatic macrocycle, where four tetrapyrrole fragments are conjugated with four benzo groups, joined by four nitrogen atoms, and which is coordinated with the metal atom. Silicon phthalocyanines (SiPc) contain two covalently bound substituents in the axial positions. Reactions of axial bonds are used for the synthesis of various silicon trialkylsiloxy- or -alkoxy-phthalocyanines, polysiloxanes containing phthalocyanine fragments, oligomers (PcSiO)n, condensation products of the dihydroxyde PcSi(OH)2, in which parallel macrocycles are linked by axial oxygen atoms [3–8]. These compounds are characterized by high thermal and chemical stability and are widely used as sensors, optical limiters, and molecular cables [2]. Metal phtalocyanines (MPc) are capable of a variety of redox transformations. They can be reduced consecutively up to 4-charged anion MPc4– or oxidized to the mono- or dication. As proved, in the phthalocyanines of many transition metals the

N N X N N

Si

N

N X N N PcSiX2, X = Cl, OH.

additional electrons are localized in the macrocycle. Synthesis of the phthalocyanine anions and cations, their electrochemistry, electronic and ESR spectra have been explored in the past 30–40 years in detail [9–12]. The absorption spectra of the metal phthalocyanines anions are very characteristic for each anion and are characterized by high repeatability for different metals, so the electronic spectroscopy is considered as a primary method of identification of the (MPc)n– anions [12]. Ionic forms of silicon phthalocyanines were studied to a lesser extent. There are studies on the electrochemical oxidation and reduction of silicon mono-, di-, tri-, and tetraphthalocyanines, but the spectral data of the ions are not available [7,13].

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SOME DONOR-ACCEPTOR COMPLEXES

phthalocyanines react with KOH in o-xylene in the presence of the crown ether 15C5 transforming into mono- and dianions without a reducing agent [14]. A similar transformation of the electronic structure in the reaction with KOH and 15C5 proceeds also in the case of silicon di- and triphthalocyanines [15, 16]. The anions are formed as a result of the intramolecular transfer of electron density on the macrocycle from the oxygen atoms of the siloxylate (Pc)SiO– K+, the degree of charge separation increases due to solvation of K+ cation with the crown ether 15C5. Free silicon dorbitals provide a n–σ–π interaction of electron pair of the axial oxygen atom and the π-electron system of the phthalocyanine macrocycle. The possibility of such interactions across the central Si atom in the porphyrin has been shown in [17].

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A 2

1

3 300

400

500

600 λ, nm

700

800

900

Fig. 1. Changes in electron absorption spectra of the reaction mixture of PcSi(OH)2 with KOH in DMSO in the absence of air, at 20°C after (1) 24 h, (2) 48 h, (3) then after exposure to O2.

The reactions of silicon phthalocyanines at the axial ligands [14–16] with the system Mg–Me3SiCl [18] demonstrate their strong dependence on the polarity and solvating ability of the solvent used. In benzene, reduction of PcSi(OH)2 with Na occurs only in the presence of the 15C5 crown ether, in THF sodium reduces PcSi(OH)2 without the crown ether additive [19]. In THF or Py the reaction with Mg–Me3SiCl at 20°C results in the contraction of the silicon phthalocyanine macrocycle to the silicon triazatetrabenzocorrole macrocycle, while in aromatic hydrocarbons this reaction does not occur even at 150°C [18].

two doublets at the wavelength ~540, 580 and ~750, 830 nm (Fig. 1, curve 3).

It seemed interesting to explore the features of transformation of electronic structure of the silicon phthalocyanines PcSiX2 (X = Cl, OH) in the reaction with KOH in DMSO, a donor polar solvent (dielectric constant 45, the donor number 29.8). It is known that deprotonting and dehydrating activity of KOH in DMSO significantly increases due to solvation of K+ with the DMSO molecules [20].

(3)

Silicon phthalocyanines PcSiX2 (X = Cl or OH) react with KOH in DMSO at room temperature, which allows monitoring this reaction through the changes in the electronic spectra of the reaction mixture. The reaction takes place equally in the presence and in the absence of the crown ether 15C5. In DMSO, as in xylene [1], the formation was observed of the paramagnetic monoanion Pc– (λmax ~580 and 620 nm, Fig. 1, curve 1) and diamagnetic dianion Pc2– (λmax 525 nm, Fig. 1, curve 2) (see the reaction scheme). The ESR signal of the monoanion is a broad single line with the g-factor close to that of free electron. The dianions both in DMSO and in o-xylene [1] react with O2 to form products with the same electronic spectra:

The reaction proceeds by the scheme: PcSi(OH)2 + KOH DMSO

[PcSi(OH)O–](K+·ДМСО) + H2O↑, –

(1)

+

[PcSi(OH)O ](K ·DMSO) + KOH DMSO

[PcSiO22–](K+·DMSO)2 + H2O↑. [PcSi(OH)O–](K+·DMSO) → – + ← [(Pc )SiO(OH)]·(K ·DMSO), I

2– + [PcSiO22–](K+·DMSO)2 → ← [(Pc )SiO2]·(K ·DMSO)2. II

(2)

(4)

The anions I and II are formed as a result of intramolecular transfer of the electron density on the macrocycle from the axial potassium siloxylate ligands (Pc)SiO– K+, the degree of the charge separation in the latter increases due to solvation of the K+ cation by DMSO molecules. The H2O produced in the reactions (1) and (2) was removed in a vacuum, together with some amount of DMSO. Unexpectedly we found that in the reaction of PcSiX2 with a suspension of KOH in DMSO the reaction mixture turns red just at mixing the reagents, and the electronic spectrum of the mixture is identical to the spectrum of the product in the reaction of dianion with oxygen (Fig. 2, curve 1). We have assumed that the formed dianion Pc2– is linked into a complex with the parent PcSiX2, and have performed a reaction of PcSiCl2 with a specially prepared Pc2–

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dianion. The spectrum of the product of this reaction was identical to the spectrum of the product at the initial stage of the reaction of PcSiX2 with KOH (Fig. 3, curve 4).

A 2 1

300

400

500

600 λ, nm

700

800

900

Fig. 2. Changes in electron absorption spectra of the reaction mixture of PcSiCl2 with KOH in DMSO in the absence of air at 20°C (1) after 5 and 60 min, (2) then after the reaction with Me3SiCl.

A 1

4

2 3

400

500

600

700 λ, nm

800

900

1000

Fig. 3. Changes in electron absorption spectra of the reaction mixture of PcSi(OH)2 with KOH in DMSO in the absence of air at 40°C (with intermittent removal of H2O) after (1) 0.5 h, (2) 1.0 h, (3) 4.0 h, and (4) after reaction with PcSiCl2.

A 1

2 3 4 400

500

600

700 λ, nm

800

900

1000

Fig. 4. Changes in electron absorption spectra of the complex [(Pc2–)·O2] in o-xylene at 20°C after (1) 10 and 120 min and at 100°C after (2) 5 min, (3) 15 min, and (4) 30 min.

We found that the reaction product of dianion Pc2– with O2 formed in o-xylene by the method [1] was stable at room temperature, its electronic spectrum remained unchanged after keeping the product for several hours. However, at 100°C the electronic spectrum of the product changed substantially, the absorption band of dianion Pc2– (λmax 524 nm, Fig. 4) appeared and gradually increased. Obviously, the reaction product of Pc2– and O2 is a complex, from which the dianion can be regenerated by removing O2 at heating in a vacuum. Identity of the electronic spectra of the products of reaction of the dianion with either O2 or PcSiX2 indicates similarity of these products. The products are likely the charge-transfer complexes in which the dianion Pc2– is a donor of electron density, and O2, PcSiCl2, or PcSi(OH)2 are acceptors [21]. In the ground state the extra electrons of the dianion Pc2– are localized on the 1eg(π*) orbital, which in phthalocyanine PcSiX2 is the lowest vacant orbital [12]. It is obvious that a partial electron transfer from the occupied 1eg(π*) orbital of the dianion Pc2– on the vacant 1eg(π*) orbital of the phthalocyanine PcSiX2 is possible, and DMSO stabilizes the formed polar complex [(Pc2–)·PcSiX2]. A large number of transition metal complexes are known that bind O2 [22]. In [23] Mn(II) phthalocyanine was shown to form an adduct with molecular O2, which was converted further into the μ-oxo-bisPcMn(III) [23]. Recently it was shown that the reversible binding of O2 by non-transition metal complexes was activated by the redox-active organic ligands, and coordination of the complexes with O2 led to the formation of peroxide bond SbO–OC and bicyclic peroxide [24]. The first stage of these reactions is electron transfer from the metal atom or catechol ligand onto the antibonding π-orbital of O2. Apparently, in the complex [(Pc2–)·O2] also occurs a partial electron transfer from the 1eg(π*) orbital of the Pc2– dianion onto the antibonding π-orbital of O2, and DMSO stabilizes the complex. The complexes of dianion Pc2– with O2 or PcSiX2 do not exhibit an ESR signal. When the complex [(Pc2–)·PcSiX2] was stored in a sealed ampule at room temperature within few days, its

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red color remained virtually unchanged, but the changes in the electronic spectra indicated a gradual transformation of the complex into the Pc2– dianion. At the increase in the temperature to 40°C and intermittent removal of H2O the transformation is finished within a few hours (Fig. 3, 3), and the resulting dianion Pc2– again formed the complex [(Pc2–)·PcSiCl2] at adding PcSiCl2 (Fig. 3 , 4). The transformation of the complexes [(Pc2–)· PcSiCl2] or [(Pc2–)·PcSi (OH)2] into the dianion Pc2– shows that PcSiCl2 or PcSi(OH)2 associated with the dianions react with KOH apparently according to the scheme of reactions (1)–(4), but the rate of these reactions is much lower. The absorption bands of the original PcSiX2 disappear from the spectrum at the start of preparation of the reaction mixture, and the formation of the dianion Pc2– from the complex [(Pc2–)· PcSiX2] takes many hours. DMSO stabilizes the polar complex [(Pc2–)·PcSiX2], which slows down formation of the dianion Pc2–. In nonpolar o-xylene this complex is not stabilized, so the reaction of PcSiX2 with KOH and 15C5 proceeds rapidly with the formation of the dianion [1]. The reaction of the complex [(Pc2–) ·PcSiX2] with Me3SiCl, H2O or CH3COOH leads to the regeneration of the phthalocyanine (Fig. 2). The complex [Pc2–·PcSiX2] reacts with O2 with the absorption of a theoretical amount of O2, but the electronic spectrum of the reaction mixture remains practically unchanged. Obviously, the O2 displaces PcSiX2 in the complex, and the complex is then converted at the action of an excess of KOH into the dianion Pc2– and then into the complex [(Pc2–)·O2]. The 1H NMR signals of the protons of benzoid fragments of the phthalocyanine macrocycles in the spectrum of the complex [(Pc2–)·PcSiX2] form two multiplets, the first at δ = 8.2 – 7.8 ppm (1), the second at δ = 7.6 – 6.9 ppm (2), the signals intensities are approximately the same (I1 ≅ I2). The reaction of this complex with O2 for 90 min led to a twofold decrease in the relative signal intensity of (1) (I1 / I2 ≅ 1/2), and after increasing the reaction duration to 24 hours the signal (1) intensity fell to almost zero. Obviously this indicates almost complete substitution of PcSiCl2 by oxygen, and in the 1H NMR spectrum remained only the signals of the complex dianion [(Pc2–)·O2]. This means that in the 1H NMR spectrum of the complex [(Pc2–)·PcSiX2] the signal (1) (δ = 8.2 – 7.8 ppm) belongs to the protons of acceptor PcSiX2, while the signal (2) (δ = 7.6 – 7.1 ppm) to the protons of the donor Pc2–.

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The reaction of Pc2– with O2 occurs at a ratio close to unity, the complex [(Pc2–)·O2] has the structure 1:1. In the reaction of the complex with Me3SiCl, H2O, or CH3COOH the regeneration of the phthalocyanine is observed and the liberation of O2, the amount of the latter is close to the theoretical value for the 1:1 complex. The regeneration of the dianion at heating the complex in a vacuum at a temperature of 35–40°C was not found, the higher temperatures were not used because of possible decomposition of DMSO. At storing the complex [(Pc2–)·O2] in O2 atmosphere the spectrum did not change, but the intensity of the signals gradually decreased, there was an irreversible degradation of the complex with the formation of a product insoluble in DMSO, apparently, of polymeric nature. In the 1H NMR spectra the signals of benzoid fragments of the complexes [(Pc2–)·PcSiX2] and [(Pc2–)·O2] are located at δ = 8.2–6.9 ppm indicating the absence of a common chain of π-conjugation in the macrocycle of the complexes. It is known that the signals of aromatic protons of the phthalocyanines are shifted downfield due to ring current in the macrocycle, to δ = 9.6–8.3 ppm [8]. It is obvious that the loss of aromatic character of phthalocyanine macrocycle in the complexes is compensated by the energy of solvation of these complexes with DMSO molecules, which results, in particular, in a much higher solubility of the complexes compared to the original PcSiX2. On the other hand, benzoid fragments resistant to O2 in the initial phthalocyanines apparently become sensitive to O2 in the complex [(Pc2–)·O2], which leads to the degradation of the complex. Further study will show how this happens. The IR spectrum of the complex [(Pc2–)·O2], like the spectrum of the complex [(Pc2–)·PcSiX2], gives little information, since it is almost completely overlapped by strong absorption bands of DMSO. Thus, the solvation of K+ cations by DMSO molecules activates KOH in the reaction with silicon phthalocyanines PcSiX2 and increases the degree of charge separation in the formed siloxylates PcSi(Oδ–Kδ+)2, that leads to the transformation of phthalocyanine into dianion even at room temperature. The dianion, which is a non-aromatic 20-π-electronic system, donates with electron density the acceptors PcSi(OH)2, PcSiCl2, or O2, which have suitable symmetry and the LUMO energy. The donor–acceptor complexes [(Pc2–)·PcSiX2] and [(Pc2–)·O2] are stabilized by polar molecules of

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DMSO, they have the same electron absorption spectra and show no ESR signal. Oxygen reacts with the [(Pc2–)· PcSiX2] complex replacing PcSiX2 and forming a D–A complex [(Pc2–)·O2]. PcSiX2 and O2 can be regenerated from the complexes by reacting it with Me3SiCl, H2O or CH3COOH. In O2 atmosphere the complex [(Pc2–) ·O2] slowly degrades with the formation of a product, whose nature has not yet been elucidated. EXPERIMENTAL Electron absorption spectra were recorded on a Perkin Elmer Lambda 25 spectrometer, 1H NMR spectra, on a Bruker DPX 200 spectrometer, ESR spectrum, on a Bruker EMX-8/2.7 instrument. Analysis was performed on a POLARIS Q/TRACE GC ULTRA vapor phase chromato-mass spectrometer. We used capillary column TR 5 MS, of 60 m length and 0.25 mm diameter. Samples 1 ml by volume were injected with a syringe into the chromatograph inlet heated to 300°C. The carrier gas (helium M 60 grade) flow rate was 1 ml min–1. The column temperature was varied from 60 to 300°C. The mass-chromatograms were registered in the range of mass numbers from 12 to 50. Phthalocyanines PcSiCl2 and PcSi(OH)2 were prepared using the technique described in [6]. DMSO was dried over Na2SO4 and distilled in a vacuum, o-xylene was dried and distilled over Na. KOH of chemically pure grade was used. O2 was obtained by thermal decomposition of KMnO4. Reactions were carried out in ampules fused either with a cell for measuring electron absorption spectra, or with tubes for obtaining NMR or ESR spectra; a magnetic stirrer was used for stirring the reaction mixture. KOH was used as a suspension in DMSO. Experiments in the absence of oxygen were carried out in sealed ampules, the reagents (PcSiX2 and KOH) after separate evacuation were mixed in the ampule. Experiments in the presence of oxygen were carried out in ampules connected to a cylinder with O2, oxygen consumption was determined using a mercury manometer. Most experiments were carried out at 20– 50°C, experiments in o-xylene at heating to 100–150°C. In a single experiment was used 1 to 100 mg of PcSiX2, 5 to 100 mg of KOH, 10 to 20 ml of DMSO. Some experiments were carried out in cells with a 0.5 mg sample of PcSiX2, 5 to 10 mg of KOH, and 5 ml of DMSO.

The reaction was monitored by observing the changes in the absorption spectrum of the reaction mixture in the UV and visible region. High boiling point of DMSO (189°C at 760 mm Hg) allowed to remove the liberated H2O, together with small amounts of DMSO, by connecting the system to the vacuum in the course of the reaction. Synthesis and some reactions of the complex [(Pc2–)·PcSiX2]. a. 0.5 mg of PcSi(OH)2 was stirred with a suspension of 10 of mg KOH in 5 ml DMSO at 20°C in the absence of air. The changes in the electronic spectra of the reaction mixture in 5 and 60 min after mixing the reagents and then after the reaction with 15–20 mg of Me3SiCl are shown in Fig. 2. b. 0.5 mg of PcSi(OH)2 and 10 mg of KOH suspended in 5 ml of DMSO were stirred in the absence of air at 40°C, with intermittent removal in a vacuum of the H2O liberated in the reaction. After 4 h, to the formed dianion Pc2– was added in the absence of air a solution of 0.1 mg of PcSiCl2 in 0.5 ml of DMSO. Changes in the electronic spectra of the reaction mixture are shown in Fig. 3. c. 20 mg of PcSiCl2 and a suspension of 30 mg of KOH in 10 ml of DMSO was stirred in the absence of air for 60 min, then to the ampule was added O2 (110 mm Hg) and the content was stirred at 20°C while measuring the O2 pressure. Consumption of O2 after 60 minutes was about 40% of the amount corresponding to taken PcSiCl2, after 20 h ~95%. Synthesis and some reactions of the complex [(Pc2–)·O2]. a. 1.5 mg of PcSi(OH)2 and a suspension of 10 mg of KOH in 5 ml of DMSO was stirred in the absence of air at 20°C. Changes in electronic spectra of the reaction mixture after 24 h, 48 h, then after exposure to O2 (100 mmHg) are shown in Fig. 1. b. 0.5 mg of PcSi(OH)2 was heated in a quartz cell with 10 mg of KOH and 10 mg of crown ether 15C5 in 10 ml of o-xylene at 170°C in the absence of air, with intermittent removing the liberated H2O in a vacuum. After 15 min the cell was cooled, O2 was introduced to the resulting dianion, the mixture was stirred for 15 min and then the O2 excess was removed. The cell was kept at 20°C for 120 min, then at 100°C for 5, 15, and 30 min. Changes in the electronic spectra of the reaction mixture are shown in Fig. 4. c. 100 mg (0.16 mmol) of PcSiCl2 was heated with 160 mg of KOH in 30 ml of DMSO in the absence of air at 40°C, with intermittent removing the formed

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H2O. After 30 h the reaction mixture became dark red. To the ampule was added O2 (150 mm Hg), and the mixture was stirred at 20°C for 90 min. The consumption of O2 was 0.16 mmol, which equals to the molar amount of taken PcSiCl2, that is, corresponded to the quantity of the formed Pc2– dianion. A reference experiment of measuring the pressure drop at a contact with O2 of KOH and DMSO without the addition of phthalocyanine showed that the amount of physically absorbed O2 can be neglected. Into the complex was condensed in a vacuum 150 mg of Me3SiCl, the mixture was stirred for 30 min, and Me3SiCl excess was removed. The reaction mixture was treated and washed with water, the precipitate was dried in a vacuum. In the IR spectrum there was no absorption band of Si–Cl (465 cm–1), there were the bands of PcSi–OH (838 cm–1 and 3470 cm–1), Si–Me (1247 cm–1) and the characteristic absorption bands of phthalocyanines (911 , 1038, 1079, 1120, 1166, 1290, 1335, 1520, 1611 cm–1). d. Determination of O2 in the products of reaction of the complex [(Pc2–)·O2] with Me3SiCl. PcSiCl2, 20 mg (0.032 mmol) and a suspension of KOH, 20 mg, in 7 ml DMSO were evacuated separately, O2 was fed into the ampule (160 mm Hg) and the reagents were mixed. The O2 consumption for 4 h at 20°C was equimolar to 95% of PcSiCl2 taken in the reaction. Solution of the complex was centrifuged to separate the excess of KOH, poured into an empty ampule with a Teflon valve, and evacuated for 30 min to remove free O2. Then into the ampule was condensed 20–30 mg (0.2– 0.3 mmol) of Me3SiCl, and the reaction mixture was stirred at 20°C for 60 min. Then helium was fed to the ampule to the pressure 1.5 atm, and the gas mixture was analyzed by the GC–MS method. For the estimation of the amount of O2 in the gas mixture the same analysis was conducted of the mixture of helium with a known content of O2. A comparison of peak areas of the ion O2 (mass number 32) in the mass chromatograms allowed to estimate the partial pressure of oxygen in the ampule and, consequently, the yield of O2 in the reaction of the complex [(Pc2–)·O2] with Me3SiCl, which amounted to 0.028–0.032 mmol (90 ± 10%). e. PcSiCl2, 10 mg (0.016 mmol), was stirred with a suspension of KOH, 15 mg, in 10 ml of DMSO in the presence of O2 (60 mm Hg) for 120 min, then the device was sealed and kept at 20°C for 30 days, during which the color of the reaction mixture changed from red to greenish-yellow, and at the bottom of the

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ampule formed a reddish thread-like precipitate. After the experiment, in the electronic spectrum of reaction mixture the absorption of the complex [(Pc2–)·O2] was not observed. 1

H NMR spectra of the complexes (DMSO-d6, δ, ppm). a. Complex [(Pc2–)·PcSiCl2]: The reaction of 6.0 mg of PcSiCl2 with 10 mg of KOH in 5 ml of DMSO-d6 was performed at 20°C in a Schlenk ampule fused with two NMR tubes. PcSiCl2 and a suspension of KOH were placed into different sections, the ampule was evacuated and sealed. Then the suspension of KOH was poured into the section containing PcSiCl2 and the reaction mixture was stirred for 75 min. In the 1H NMR spectrum of the complex there are two groups of protons: δ = 8.2–7.8 ppm (1) and δ = 7.6– 7.1 ppm (2), intensity ratio of the signals (1) and (2) was close to unity. b. Complex [(Pc2–)·O2]: To the residue of the reaction mixture in the Schlenk ampule was added O2 (150 mm Hg), and the mixture was stirred for 90 min. The intensity ratio of the signals (1) and (2) in the 1H NMR spectrum has changed to 1:2. The NMR tube was kept under oxygen for 24 h and the spectrum was registered again. Signal (1) fell almost to zero. REFERENCES 1. Phthalocyanines: Properties and applications, vols. 1– 4, Leznoff, C.C. and Lever, A.B.P, Eds., New York: VCH, 1989–1996. 2. McKeown, N.B., J. Mater. Chem., 2000, vol. 10, p. 1979. 3. Meyer, G. and Wöhrle, D., Makromol. Chem., 1974, vol. 175, p. 714. 4. Davison, J.B. and Wynne, K.J., Macromolecules, 1978, vol. 11, p. 186. 5. Ritter, G.W. and Kenney, M.E., J. Organomet. Chem., 1978, vol. 157, p.75. 6. Dirk, C.W., Inabe, T., Schoch, K.F., Jr., and Marks, T.J., J. Am. Chem. Soc., 1983, vol. 105, p. 1539. 7. Wheeler, B.L., Nagasubramanian, G., Bard, A.J., Schechtman, L.A., Dininny, L.R., And Kenney, M.E., J. Am. Chem. Soc., 1984, vol. 106, p. 7404. 8. Silver, J., Sosa-Sandez, J.L., and Frampton, Ch.S., Inorg. Chem., 1998, vol. 37, p. 411. 9. Shablya, A.V. and Terenin, A.N., Optika i Spektroskopiya, 1960, vol. 9, p. 533. 10. Clack, D.W. and Yandle, J.R., Inorg. Chem., 1972, vol. 11, p. 1738. 11. Sidorov, A.N. and Maslov, V.G., Usp. Khim., 1975, vol. 44, p. 571.

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12. Minor, P.C., Gouterman, M., and Lever, A.B.P., Inorg. Chem., 1985, vol. 24, p. 1894. 13. DeWulf, D.W., Leland, J.K., Wheeler, B.L., Bard, A.J., Batzel, D.A., Dininny, D.R., and Kenney, M., Inorg. Chem., 1987, vol. 26, p. 266. 14. Myakov, V., Chudakova, V., and Lopatin, M., J. Porphyrins Phthalocyanines, 2001, vol. 5, p. 617. 15. Myakov, V.N., Kuropatov, V.A., Lopatina, T.I., and Sedelnikova, V.N., J. Porphyrins Phthalocyanines, 2002, vol. 6, p. 336. 16. Myakov, V.N., Lopatin, M.A., and Kurskii, Yu.A., J. Porphyrins Phthalocyanines, 2003, vol. 7, p. 176. 17. Zheng, J.-Yu., Konishi, K., and Aida, T.A., J. Am. Chem. Soc., 1998, vol. 120, p. 9838. 18. Myakov, V.N., Kurskii, Yu.A., Sedel’nikova, V.N., Makhrova, T.V., and Lopatin, M.A., Koord. Khim., 2008, vol. 34, no. 7, p. 528.

19. Myakov, V.N., Kuropatov, V.A., and Lopatina, T.I., Koord. Khim., 2009, vol. 35, p. 193. 20. Gutman, V., Khimiya koordinatsionnykh soedinenii v nevodnykh rastvorakh (Chemistry of Coordination Compounds in Non-Aqueous Solution), Moscow: Mir, 1971, ch. VII. 21. Gur’yanova, E.N., Gol’dshtein, I.P., and Romm, I.P., Donorno-aktseptornaya svyaz’ (Donor-Acceptor Bond), Moscow: Khimiya., 1973, ch. 1. 22. Chemical Revs., 1994, vol. 94, no. 3. 23. Elvidge, J.A. and Lever, A.B.P., Proc. Chem. Soc., 1959, p. 195. 24. Cherkasov, V.K., Abakumov, G.A., Grunova, E.V., Poddelsky, A.I., Fukin, G.K., Baranov, E.V., Kurskii, Yu.A., and Abakumova, L.G., Chem. Eur. J., 2006, vol. 12, p. 3916. 25. Gutman, V., Coordination Chemistry in Non-Aqueos Solutions, New York: Springer-Verlag, 1968, ch. 7.

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