Phthalocyaninato Copper Research Articles

Electron and Ion Transport in Mixed Electrochromic Thin Films of Perfluorinated Phthalocyanines

Thin films of a mixture of the perfluorinated phthalocyanines 1,2,3,4,8,9,10,11,15,16,17,18,22,23,24,25-hexadeca-fluorophthalocyaninato copper(II) (F16PcCu) and 1,4,8,11,15,18,22,25-octakis-fluoro-2,3,9,10,16,17,23,24-octakis-perfluoro(isopropyl) phthalocyaninato copper(II) (F64PcCu) of different thicknesses and mixing ratios were prepared by simultaneous vapor deposition. A moderate extent of the intermolecular coupling between F16PcCu and F64PcCu within the mixed films comparable to that reported earlier for tetrakisperfluoroisopropyl-perfluoro phthalocyanine (F40PcCu) was revealed by UV/Vis spectroscopy. The electrochromic properties as well as the transport of electrons and counter cations in the 1:1 F16PcCu:F64PcCu mixed films were investigated by electrochemical and spectroelectrochemical characterization using an aqueous solution of KCl as electrolyte. The transport coefficients of electrons and ions of these films were comparable to those reported for F40PcCu films, for which a well-balanced, equally fast transport of both electrons and ions had been seen. Fast, reversible, and stable switching characteristics of the mixed films, upon reduction and intercalation of K+ counterions and re-oxidation with extraction of the counterions, were observed by cyclic voltammetry, chronoamperometry, and simultaneously measured optical absorption spectra.

Discotic liquid crystals of transition metal complexes 56: Synthesis of mesogenic phthalocyanine-fullerene dyads and influence of the substitution position of alkoxy chains and the kind of terminal groups on appearance of the helical supramolecular structure

We have synthesized twelve novel discotic columnar liquid crystals based on a phenoxy-group-substituted phthalocyaninato copper(II) complex having the same alkoxy chain of C[Formula: see text]H[Formula: see text]O at different positions in the phenoxy group: the parent compounds {0a~0c-16}and the OH-substituted compounds {3a~3c-16}, the OFBA-substituted compounds {2a~2c-16}and the C[Formula: see text]-substituted dyads {1a~1c-16}. The letters of a, b and c mean substitution positions of C[Formula: see text]H[Formula: see text]O group at [Formula: see text], [Formula: see text] and [Formula: see text], respectively. We have investigated the influence of both substitution position of the alkoxy chains and the kind of terminal groups (OH, OFBA and C[Formula: see text] on the mesomorphism and the helical supramolecular structure, by using DSC, POM and temperature-variable small angle X-ray diffraction measurements. As a result, an additional big peak (Peak H) tends to appear at around 2[Formula: see text] = 1.1[Formula: see text] in the X-ray diffraction patterns only for the dyads {1a~1c-16}but not for the other compounds, {0a~0c-16}, {3a~3c-16}and {2a~2c-16}, regardless of the substitution positions of the alkoxy group. Moreover, we revealed that both the m-substituted derivative 1a-16 and the m,p-substituted derivative 1c-16 gave Peak H, but that only the p-substituted derivative 1b-16 did not give Peak H among these three dyads {1a~1c-16}. From the temperature-variable small angle X-ray diffraction measurements for the m,p-substituted derivative 1c-16 using two different sample preparation methods, we proved that the Peak H originates from a helical pitch of fullerenes. We also pointed out that the m-substituted long alkoxy chains are at least needed to form the helical supramolecular structure in the present (PhO)[Formula: see text]PcM-C[Formula: see text]-based dyads.

Discotic liquid crystals of transition metal complexes, 53†: synthesis and mesomorphism of phthalocyanines substituted by m-alkoxyphenylthio groups

We have successfully synthesized a series of novel octakis([Formula: see text]-alkoxyphenylthio)phthalocyaninato copper(II) complexes, ([Formula: see text]-C[Formula: see text]OPhS)[Formula: see text]PcCu ([Formula: see text] = 2, 4, 6, 8, 10, 12, 14, 16: 1b~1i), by our developed method to reveal their mesomorphism. The phase transition behavior and mesophase structures have been established by using a polarizing optical microscope, a differential scanning calorimeter, and a temperature-dependent small angle X-ray diffractometer. Interestingly, the very short chain-substituted derivatives, ([Formula: see text]-C[Formula: see text]OPhS)[Formula: see text]PcCu (1a) and ([Formula: see text]-C[Formula: see text]OPhS)[Formula: see text]PCu (1b), show a hexagonal ordered columnar (Col[Formula: see text] mesophase, whereas each of the other longer-chain-substituted derivatives, ([Formula: see text]-C[Formula: see text]OPhS)[Formula: see text]PcCu ([Formula: see text] = 4~16: 1c~1i), shows only rectangular ordered columnar (Col[Formula: see text] mesophase(s). In contrast to the present longer-chain-substituted phenylthio derivatives, each of the previous longer-chain-substituted phenoxy derivatives, ([Formula: see text]-C[Formula: see text]OPhO)[Formula: see text]PcCu ([Formula: see text] = 10–20), shows a different columnar mesophase of Col[Formula: see text]. We discuss this difference of mesomorphism from the viewpoint of the different steric hindrance originated by the peripheral substituents, PhO and PhS groups. Moreover, we could estimate the optical band gaps of ([Formula: see text]-C[Formula: see text]OPhO)[Formula: see text]PcCu and ([Formula: see text]-C[Formula: see text]OPhS)[Formula: see text]PcCu (1f) from absorption edge of the Q-bands to be 1.79 eV and 1.70 eV, respectively. Therefore, the phenylthio-substituted derivative gave a narrower band gap byca. 0.1 eV in comparison with the phenoxy-substituted derivative.

Flying-seed-like liquid crystals 7: Synthesis and mesomorphism of novel octakis(m-chloropyridyloxy) phthalocyanato copper(II) complexes

We have synthesized three novel octakis([Formula: see text]-chloropyridyloxy)phthalocyaninato copper(II) complexes, [x-PyO(m-Cl)][Formula: see text]PcCu([Formula: see text] [Formula: see text] 2, 3, 4: 2a–2c), keeping a chlorine atom at the meta position on the 2-, 3- and 4-pyridyloxy group, in which the nitrogen atom is located at the 2-, 3- and 4-positions, respectively. Their phase transition behavior and the mesophase structure have been established by using a polarizing optical microscope, a differential scanning calorimeter, and a temperature-dependent small angle X-ray diffractometer. Very interestingly, the mesomorphism appears with strong dependence of the position of nitrogen in [Formula: see text]-chloropyridyloxy group. The derivative [3-PyO(m-Cl)][Formula: see text]PcCu (2b) introduced a nitrogen atom at the 3-position is not mesogenic but crystalline. On the other hand, the derivative [2-PyO(m-Cl)][Formula: see text]PcCu (2a) introduced a nitrogen atom at the 2-position shows columnar mesomorphism only at very high temperatures over 325°C. The derivative [4-PyO(m-Cl)][Formula: see text]PcCu (2c) introduced a nitrogen atom at the 4-position shows columnar mesomorphism in a very wide temperature region from rt to the decomposition temperature at 306°C. From the viewpoint of N…Cl halogen bond, we have discussed about relationship between their mesomorphism and the position of nitrogen atom in [Formula: see text]-chloropyridyloxy group.

Flying-seed-like liquid crystals 5: Liquid crystals based on octakisphenylthiophthalocyanine and their optical properties

We have synthesized three novel flying-seed-like liquid crystals based on phthalocyaninato copper(II) (abbreviated as PcCu ) substituted by bulky groups {(o- C1) PhS (i), (m- C1) PhS (j), [m, p-( C1)2] PhS (k)} instead of using long alkyl chains, in order to investigate their mesomorphism. Their phase transition behavior and the mesophase structures have been established by using a polarizing optical microscope, a differential scanning calorimeter, and a temperature-dependent small angle X-ray diffractometer. As the results, [(o-C1)PhS]8PcCu (8i), [(m-C1)PhS]8PcCu (8j) and {[m,p-(C1)2]PhS}8PcCu (8k) show a Coltet.omesophase at 314.9~362.9 °C, a Colro(P2m) mesophase at 287.4~334.2°C and a Colro(P2m) mesophase at 331.8~386.8°C, respectively. Very interestingly, each of the derivatives thus exhibits a columnar mesophase at very high temperatures. The mesomorphism is apparently originated from the novel bulky groups (i~k). It is also noteworthy that the Q-bands of the present PhS-containing Pc derivatives 8i~8k in THF significantly red-shift by about 35 nm in comparison with those of the corresponding PhO-containing derivatives in THF.

Switching of the Rate-limiting Step in the Electrochromic Reduction of Fluorinated Phthalocyanine Thin Films by Decreased Intermolecular Coupling

Thin solid films (5-120nm) of the electron deficient perfluorinated phthalocyanine 1,2,3,4,8,9,10,11,15,16,17,18,22,23,24,25-hexadeca-fluorophthalocyaninato copper(II) (F16PcCu) and the perfluoroalkyl-substituted perfluorophthalocyanine 1,4,8,11,15,18,22,25-octakis-fluoro-2,3,9,10,16,17,23,24-octakis-perfluoro(isopropyl) phthalocyaninato copper(II) (F64PcCu) have been prepared by physical vapor deposition onto a glass substrate coated with a transparent conductor (indium-tin-oxide, ITO). Cyclic voltammetry, chronoamperometry and spectroelectrochemical UV-vis spectroscopy studies revealed that the films were readily reduced and re-oxidized at potentials slightly negative of the Ag/AgCl reference electrode confirming a significant stabilization of the produced anions by the electron-withdrawing fluorinated substituents. A significant color change accompanied the change of the molecular redox states. Electroneutrality of the films was ensured by intercalation of K+-counter ions upon reduction and their ejection upon re-oxidation. Molecules of F64PcCu were reduced by one electron, those of F16PcCu by up to two, for thin films subjected to slow charging rates. In addition to a decisive influence on the electronic structure of the inner ring π-system of the metal complexes the steric hindrance of the fluorinated ligands influence the extent of intermolecular coupling. The perfluoroalkyl, Rf, groups in F64PcCu thereby led to widely decoupled electronic states of the molecules in the thin films as detected by the observed optical absorption spectra. The bulky Rf groups also led to facile diffusion of the K+-counter ions into the films, as well as to a significantly reduced electrical conductivity of F64PcCu relative to F16PcCu. Time-resolved measurements served to analyze the interplay of the two mandatory transport processes. Interestingly, the variability in steric hindrance results in a qualitative change in the rate-limiting steps of the reduction. Thus, in the case of F64PcCu the transport of electrons in the molecular films is rate-limiting, as opposed to counter ion diffusion in the case of F16PcCu. This switch underlines the importance of structural parameters for the tuning of the observed reduction and re-oxidation of organic thin films via intermolecular interactions.

Helical self-assembly of optically active phthalocyanine derivatives in mesophase. Effect of the position of chiral substituents on the handedness and mesophase textures

Two phthalocyanine derivatives with peripheral chiral (S)-2-methylbutanol moieties on the α- or β-position of the phthalocyanine ring, namely {(1,8,15,22-tetra[(S)-2-methylbutoxy]} phthalocyaninato copper complex (S)-CuPc(α-OC5H11)4 (1) and {(2,3,9,10,16,17,23,24-octa[(S)-2-methylbutoxy]} phthalocyaninato copper complex (S)-CuPc(β-OC5H11)8 (2) were synthesized. Their helical self-assembly behavior in mesophase were comparatively investigated by electronic absorption and circular dichroism spectroscopy, differential scanning calorimeter, polarized optical microscope and X-ray diffraction technique. In mesophase, (S)-CuPc(α-OC5H11)4 (1) self-assembled into rectangular columnar liquid crystals with left-handed fan texture. However, hexagonal columnar liquid crystals with well-ordered, rare, right-handed spherulites were formed from (S)-CuPc(β-OC5H11)8 (2). These results clearly indicated the effect of the position of chiral substituents on the handedness and mesophase textures of self-assembled liquid crystals and will be helpful towards rational design and preparation of chiral liquid crystal materials.

Peripheral modification and basicity of (phthalocyaninato)-copper(II) according to the electronic spectroscopy and quantum chemical calculation data

Singly, doubly, and triply protonated forms of tetra- and octacarboxy (phthalocyaninato)copper(II) derivatives were identified and characterized by electronic absorption spectra and PM3 quantum chemical calculations. Molecules of carboxy-substituted phthalocyanine copper(II) complexes have a distorted nonplanar structure with specific charge distribution over meso-nitrogen atoms. Singly, doubly, and triply protonated complexes at the meso-nitrogen atoms and carboxy groups exist as mixtures of isomers, which is reflected in splitting of the Q band in the electronic absorption spectra and reduction of its symmetry. The formation of bifurcated hydrogen bonds O ... H+ ... Nmeso and O ... H+ ... O between the neighboring substituents was revealed.

Solution-processable ambipolar organic field-effect transistor based on Co-planar bisphthalocyaninato copper

A soluble binuclear phthalocyaninato copper (II) complex, Cu2[Pc(COOC8H17)6]2 (1), with planar molecular structure and extended conjugation system, has been designed and synthesized. By fusing two phthalocyanine rings side by side and introducing electron withdrawing groups at periphery positions, the energy levels of HOMO and LUMO have been tuned successfully into the range of an air-stable ambipolar organic semiconductor required as revealed by the electrochemical studies. With the help of a solution-based quasi-Langmuir–Shäfer (QLS) method, thin solid films of this compound were fabricated and organic field effect transistors (OFETs) based on these QLS thin solid films were constructed. Because of the promising electrochemical properties as well as the high ordered packing structure of the molecules in the thin solid films, the OFETs performed excellent ambipolar operating properties, with the electron and hole mobility in air as high as 1.7×10−1 and 2.3×10−4cm2V−1s−1, respectively. For comparison purpose, mononuclear compound Cu[Pc(COOC8H17)8] (2) was comparatively studied. The QLS thin solid films of this compound possess similar ordered structure with that of Cu2[Pc(COOC8H17)6]2 (1), but the OFETs based on the thin solid films of this compound can only show n-type properties under nitrogen atmosphere with an extremely small electron mobility of 1.6×10−4cm2V−1s−1. This result suggests that extension on the conjugation system of an aromatic compound with multiple electron withdrawing groups can tune the molecule into an air stable ambipolar organic semiconductor.

Structure and properties of tetrakis[3(4)-chlorophthalocyaninato]copper(II) protonated forms in the isolated state and in the sulfuric acid solutions

Results of the quantum-chemical PM3 and experimental spectrophotometric studies of the stepwise protonation of tetrakis[3(4)-chlorophthalocyaninato]copper(II) are presented. The number, structure, and energy characteristics of consecutively protonated isolated molecules of the substituted complexes have been determined; the stability and electron absorption spectra of the complexes protonated forms in concentrated sulfuric acid solution have been studied. The special effect of substitution with halogen on the electronic structure of the exocyclic nitrogen atoms of (phthalocyaninato)copper(II) has been examined.

Helical self-assembly and nonlinear optical properties of optically active phthalocyanine derivatives bearing eight optically active diethyleneglycol mono-(S)-2-methylbutyl ether moieties on the β-position of the phthalocyanine ring

Two phthalocyanine derivatives with eight peripheral chiral diethyleneglycol mono-(S)-2-methylbutyl ether moieties on the β-position of the phthalocyanine ring were prepared from the tetramerization of corresponding phthalonitriles, promoted by organic base 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). The self-assembly behavior of metal free phthalocyanine 1 and its copper congener 2 have been comparatively investigated by electronic absorption and circular dichroism (CD) spectroscopy, scanning electron microscopy (SEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The metal free phthalocyanine 1 self-assembles into the right-handed screw-like aggregates (ca. 10 μm length, 6 μm width, and 1.5 μm helical pitch), while, phthalocyaninato copper 2 self-assembled into left-handed fibrous aggregates (ca. 25 μm length, 1 μm width, and 0.7 μm helical pitch). These results indicated the effect of metal-coordination bonds on the morphology and handedness of the self-assembled nanostructures. Further, excellent nonlinear optical (NLO) properties of both compounds were also revealed by a Z-scan experiment, which expand their applications in nonlinear optics.

Discotic liquid crystals of transition metal complexes 46: mesomorphism and antagonist solubility of octaphenoxy-phthalocyaninato copper(II) complex substituted by oligoether chains

We synthesized a novel discotic liquid crystalline compound, octakis[3-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)phenoxy]phthalocyaninato copper(II) (abbreviated as [m- MeO(EtO)3PhO]8PcCu ), and established the mesomorphism by using a differential scanning calorimeter, a polarizing optical microscope, and temperature-dependent wide angle X-ray diffraction diffractometer. Very interestingly, this [m- MeO(EtO)3PhO]8PcCu complex showed a hexagonal ordered columnar (Colho) mesophase in the virgin sample, whereas it showed a rectangular ordered columnar (Colro(P21/a)) mesophase in the non-virgin sample. The Colho mesophase gave a dimer stacking distance at 9.26 Å, whereas the Colro mesophase gave a short monomer stacking distance at 3.45 Å. Furthermore, this novel Pc derivative is readily soluble in polar solvents such as acetone, ethanol and methanol. Using antagonist solubilities of the present hydrophilic [m- MeO(EtO)3PhO]8PcCu derivative in a polar solvent and the previous hydrophobic (C10O)16TzCu derivative in the non-polar solvent, a p-n junction layered thin films could be successfully prepared.

Discotic liquid crystals of transition metal complexes 44: synthesis of hexaphenoxy-substituted phthalocyanine derivatives showing spontaneous perfect homeotropic alignment

We have synthesized novel hexaphenoxy-substituted phthalocyanine derivatives, 2-(12-hydroxydodecyloxy)-3-methoxy-9,10,16,17,23,24-hexakis(3,4-di-n-alkoxyphenoxy)phthalocyaninato copper(II) (abbreviated as Cn(OC12OH)PcCu : n = 10, 12, 14), and investigated their columnar mesomorphism and homeotropic alignment property. These hexaphenoxy-substituted Pc derivatives could be successfully isolated and purified from the mixture products by polarity difference. It was revealed by using polarizing optical microscopic observations, differential scanning calorimetry and temperature-dependent X-ray diffraction studies that each of the hexaphenoxy-substituted Pc derivatives has plural mesophases, and that the tetragonal columnar (Coltet) mesophase shows spontaneous perfect homeotropic alignment between two non-surface-treated glass plates without any defects and polydomain boundaries.

Doping in mixed films of differently substituted phthalocyanines measured in‐situ during film growth

AbstractMixed films of unsubstituted phthalocyaninato copper (H16PcCu) and its perfluorinated derivative (F16PcCu) were prepared by co‐evaporation in different molecular mixtures. The films were analyzed in‐situ by conduction measurements. High admixtures of H16PcCu in F16PcCu films disturbed the charge transport. Optical transmission spectroscopy consequently showed the disturbance of the F16PcCu solid state structure for increased admixtures of H16PcCu. The spectral signatures of both the βbilayer‐structure and the β‐structure of F16PcCu decreased. Low admixtures of H16PcCu increased the conductivity, indicating a successful dopant interaction at widely preserved crystallinity of F16PcCu. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)

Flying-seed-like liquid crystals 2: unprecedented guidelines to obtain liquid crystalline compounds

In order to obtain novel “flying-seed-like” liquid crystals, we have prepared a series of bulky group-substituted phthalocyanine derivatives without any long alkyl chains: tetra[4-(triphenylmethyl)-phenoxy]phthalocyaninato copper(II) (1a), tetra[4-(1,1-diphenylethyl)phenoxy]phthalocyaninato copper(II) (1b), tetra[4-(1-methyl-1-phenylethyl)phenoxy]phthalocyaninato copper(II) (1c), tetra[4-(tert-butyl)phenoxy]phthalocyaninato copper(II) (1d), and octa[4-(triphenylmethyl)phenoxy]phthalocyaninato copper(II) (4). We have established by using a polarizing optical microscope, a differential scanning calorimeter and a temperature-dependent small angle X-ray diffractometer that the Pc derivatives 1a–d, but not 4, show columnar mesomorphism from r.t. to the extremely high decomposition temperatures at 450–500 °C. Their mesomorphism originates from thermal fluctuations due to free rotation of the bulky substituents. Thus, we have systematically demonstrated for the first time that liquid crystals can be also obtained by a series of novel bulky substituents instead of conventional long alkyl chains. Hence, we will be able to obtain a wide variety of new liquid crystalline compounds by using these bulky substituents instead of long alkyl chains. Very interestingly, these are unprecedented guidelines to obtain liquid crystalline compounds.

The first solution-processable n-type phthalocyaninato copper semiconductor: tuning the semiconducting nature via peripheral electron-withdrawing octyloxycarbonyl substituents

A series of unsymmetrical phthalocyaninato copper complexes simultaneously incorporating electron-withdrawing and electron-donating substituents at the phthalocyanine periphery Cu{Pc(15C5)[(COOC8H17)6]} (2), Cu{Pc[(adj-15C5)2][(COOC8H17)4]} (3), Cu{Pc[(opp-15C5)2][(COOC8H17)4]} (4), Cu{Pc(15C5)3[(COOC8H17)2]} (5) were prepared and isolated. For comparative studies, symmetrical analogues including 2,3,9,10,16,17,24,25-octakis(octyloxycarbonyl)phthalocyaninato copper complex Cu[Pc(COOC8H17)8] (1) and 2,3,9,10,16,17,24,25-tetrakis(15-crown-5)phthalocyaninato copper complex Cu[Pc(15C5)4] (6) were also prepared. Their electrochemistry was studied by cyclic voltammetry (CV) and differential pulse voltammetry (DPV). With the help of a solution-based self-assembly process, these compounds were fabricated into organic field effect transistors (OFETs) with top contact configuration on hexamethyldisilazane (HMDS)-treated SiO2/Si substrate. In line with the electrochemical investigation results, a p-type OFET with a carrier mobility (for holes) of 0.06 cm2 V−1 s−1 was shown for Cu[Pc(15C5)4] (6) with electron-donating 15-crown-5 as the sole type of peripheral substituent. In contrast, n-type devices with a carrier mobility (for electrons) of 6.7 × 10−6–1.6 × 10−4 cm2 V−1 s−1 were achieved for 1–5 with electron-withdrawing octyloxycarbonyl substituents at the peripheral positions of phthalocyanine ring, indicating the significant effect of electron-withdrawing octyloxycarbonyl substituents on tuning the nature of phthalocyanine organic semiconductors. The present results represent the first example of solution-processed n-type phthalocyanine-based OFET devices.

Novel Pathway to Synthesize Unsymmetrical 2,3,9,10,16,17,23-heptakis(alkoxyl)-24-mono(dimethylaminoalkoxyl)phthalocyanines

A new pathway by means of transetherification has been developed to synthesize novel unsymmetrical 2,3,9,10,16,17,23-heptakis(alkoxyl)-24-mono(dimethylaminoalkoxyl)phthalocyanine compounds. Cyclic tetramerization of 4,5-di(alkoxyl)phthalonitrile in refluxing dimethylamino-alcohol with high boiling point such as dimethylaminoethanol (DMAE) and 1-dimethylamino-2-propanol in the presence of lithium and pyrazino[2,3-f][1,10]phenanthroline-2,3-dicarbonitrile followed by treatment with acetic acid led to the isolation of a series of unsymmetrical metal free 2,3,9,10,16,17,23-heptakis(alkoxyl)-24-mono(dimethylaminoalkoxyl)phthalocyanine compounds H(2){Pc(OR)(7)[OR'N(CH(3))(2)]} [R = C(4)H(9), C(5)H(11), C(8)H(17) and R' = C(2)H(4); R = C(4)H(9) and R' = CH(CH(3))CH(2)] (1-4). Metal insertion into unsymmetrical metal free phthalocyanines (Pc's) using Cu(OAc)(2)·H(2)O in dimethylformamide (DMF) at 140 °C easily afforded corresponding unsymmetrical phthalocyaninato copper complexes Cu{Pc(OR)(7)[OR'N(CH(3))(2)]} (5-8) in good yields. These novel unsymmetrical phthalocyanine compounds have been characterized by a series of spectroscopic methods including (1)H NMR, electronic absorption, IR, and mass spectroscopy in addition to elemental analysis. Their electrochemistry was also studied by cyclic voltammetry (CV) and differential pulse voltammetry (DPV) methods. The present result will be helpful for designing and preparing unsymmetrical phthalocyanines with potential applications in dye-sensitized solar cells.

The influence of modification of periphery of hydroxo(phthalocyaninato)aluminum(III) and (phthalocyaninato)copper(II) on the structure and stability of the molecules as studied by computer simulation and kinetic experiment

The molecular structures of (phthalocyaninato)copper(II) and hydroxo(phthalocyaninato)-aluminum(III) molecules and their substituted analogs were calculated by PM3 quantum-chemical method. It is found that at halogen-, nitro-, halogen-nitro-, and carboxy-substitution the largest steric distortions are observed in complexes with substituents in the 3 position, and effective positive (copper complex) and negative (aluminum complex) charge on coordinated N4 at all types of substitution is increased and decreased, respectively. The kinetics of transformation at coordinational center in sulphuric acid was studied and success was demonstrated of the comparative analysis of the results of calculations and data on the influence of functional substitution on the stability of complexes in governing the mechanism and regulation of influence of substituents on the reactivity of metallophthalocyanines.

Novel phthalocyanines with naphthalenic substituents

Phthalocyanines with four naphthyl-malonic ester groups on the periphery were synthesized by cyclotetramerization of 4-(1,1-dicarbethoxy-2-(1-naphthyl)-ethyl)-phthalonitrile. The new compounds were characterized by spectroscopic methods. The electronic spectra exhibit intense π–π* transitions from the naphthyl moiety together with the characteristic Q and B bands of the phthalocyanine core. The electrochemical properties of the 2,9,17,23-tetra-(1,1-(dicarbethoxy)-2-(1-naphthyl)-ethyl) phthalocyaninato copper(II) complex were studied by cyclic voltammetry.

Discotic liquid crystals of transition metal complexes 39: columnar mesomorphism and homeotropic alignment speed of sandwich-type of double-deckers and triple-deckers based on phthalocyaninato lutetium metal complexes

A series of sandwich-type metal complexes, bis[2,3,9,10,16,17,23,24-octakis(3,4-dialkoxyphenoxy)phthalocyaninato]lutetium(III) ({[( C n O )2 PhO ]8 Pc }2 Lu (n = 8−16): double-deckers (2)), were synthesized. As the by-product, tris[2,3,9,10,16,17,23,24-octakis(3,4-diakoxyphenoxy)phthalocyaninato]dilutetium(III) ({[( C n O )2 PhO ]8 Pc }3 Lu 2 (n = 8, 9, 11, 12, 14, 16): triple-deckers (3)) were successfully separated. The mesomorphic properties of these double-deckers (2) and triple-deckers (3) were investigated using a polarization microscope, differential scanning calorimetry and temperature-dependent X-ray diffraction techniques. The double-deckers (2) showed Colh , Cub and Coltet mesophases for n ≥ 10. On the other hand, the triple-deckers (3) showed only a Colr mesophase for n = 8, only a Coltet mesophase for n = 14, and both Colr and Coltet mesophases for n = 9, 11, 12 and 16. For the Coltet mesophase, both the double-deckers (2) and the triple-deckers (3) exhibited spontaneous homeotropic alignment in a large area. In comparison with the homeotropic alignment of these present lutetium complexes 2, 3 and the previous copper complexes, 2,3,9,10,16,17,23,24-octakis(3,4-dialkoxyphenoxy)phthalocyaninato copper(II) ([( C n O )2 PhO ]8 PcCu (n = 9-14): single-decker (1)), the alignment was fast, slow and fast, respectively, in the order of the single-deckers (1), double-deckers (2) and triple-deckers (3). Very interestingly, the complexes 1 and 3 which have flat Pc macrocycles gave fast alignment, whereas the complexes, 2, which have non-flat Pc macrocycles, gave slow alignment. Thus, it was revealed for the first time that the flatness of discotic liquid crystalline molecules influences the speed of homeotropic alignment.