Search

Hitherto unknown phosphorus-containing 4,5-bis(diethoxyphosphorylmethyl)- and 4-methyl-5-diethoxyphosphorylmethylphthalonitriles were synthesized starting from o-xylene. Their tetramerization afforded free phthalocyanine ligands and their complexes with Zn, Ni, Co, and a number of rare-earth metals. The spectral and electrochemical properties of the phthalocyanines synthesized were studied.

The study is concerned with the luminescence properties of ensembles of semiconductor structures containing organic phthalocyanine molecules with erbium ions as complexing agents. The photoluminescence spectra of the structures of the type of erbium monophthalocyanine, bisphthalocyanine, and triphthalocyanine are recorded. The photoluminescence peaks are detected at the wavelengths 888, 760, and 708 nm (and photon energies 1.4, 1.6, and 1.75 eV) corresponding to electronic transitions within the organic complexes. It is found that, when a metal complexing agent is introduced into the molecular structure of the ligand, the 708 nm luminescence peak becomes unobservable. It is shown that, in the bisphthalocyanine samples, the photoluminescence signal corresponding to transitions from the 4F 9/2 level of erbium ions is enhanced.

Holographic properties, dark conductivity, and photoconductivity of films based on carbazolyl-containing cooligomer doped with zinc 2,3,9,10,16,17,23,24-octabutylphthalocyanine (PcBuZn), double-decker dysprosium phthalocyanine (Dy(Pc)2), and Pr2O3 particles were studied. The films with PcBuZn are characterized by higher photoconductivity, which is due to photogeneration of long-lived triplet charge pairs. The presence of Dy in the sensitizer molecules or Pr2O3 in the films enhances their photoconductivity, a change that is attributed to an increase in the rate of the singlet-triplet intersystem crossing of the charge pairs.

The transmittance spectra of erbium phthalocyanine complexes in the mid- and near-infrared wavelength regions are studied. A detailed identification of the transmittance lines is presented for three types of phthalocyanine complexes. Data on the absorption of electromagnetic radiation at the wavelengths around 1.5 μm due to the 4 I 13/2 → 4 I 15/2 intracenter transitions between the levels of the erbium ions incorporated into the samples are obtained. It is found that some of the mid-infrared absorption lines shift when the number of organic ligands is increased by a factor of 2 or 3. It is shown that the absorption coefficient at the wavelengths around 1.5 μm is equal to 27.5, 32.5, and 74 cm−1 for erbium monophthalocyanine, bisphthalocyanine, and triphthalocyanine, respectively.

New alkyl-substituted phosphorus phthalocyanines and triazatetrabenzocorroles were synthesized. The structures of these complexes were confirmed by 1H, 13C, and 31P NMR spectroscopy, mass spectrometry, and electronic absorption spectroscopy.

Features of the photoconductivity of films of composites based on [2-methoxy-5-(2′-ethylhexyloxy)-1,4-phenylenevinylene] with additions of zinc 2,3,9,10,16,17,23,24-octabutylphthalocyanine and C60 were studied. Luminescence quenching and an increase in the photoconductivity with the addition of C60 to their composition were detected. The increase in the photoconductivity is connected with the capture of electrons and their transport along the C60 molecules.

Methods for the selective synthesis of mono-(RPcLnOAc), di-(RPc2Ln), and triphthalocyanines (RPc3Ln2) of rare-earth metals (Ln = Lu, Er, Eu) from symmetrically substituted 2,3,9,10,16,17,23,24-octaalkylphthalocyanines RPcH2 (R = Et, Bu) were developed. The synthesized complexes were characterized by NMR spectroscopy, mass spectrometry, and electronic absorption spectra. The conditions for 1H NMR spectra recording were optimized. Regularities in changing the spectral properties of the synthesized compounds, depending on the lanthanide nature and the planarity of metal phthalocyanine complexes, were found.

New boron μ-chloro-and μ-alkoxyhexabutylsubphthalocyanines were synthesized. A heteronuclear complex containing both the phthalocyanine and subphthalocyanine fragments was prepared. The spectroscopic properties of these compounds were studied.

Semiconductor structures of the type of butyl-substituted erbium monophthalocyanine and triphthalocyanine are studied by Raman spectroscopy. It is shown that, when the sandwich-like structure of the molecule incorporating two complexing atoms between the ligands is considered instead of the planar molecular structure with one ligand and one metal atom, a series of lines appears in the Raman spectrum. In this series, the wave numbers of the lines represent an arithmetic progression with the arithmetical ratio ∼80 cm−1. It is suggested that this feature is due to the larger number of organic molecules per metal atom in the triphthalocyanine complex, and the four Raman peaks at the frequencies 122, 208, 280, and 362 cm−1 are the manifestation of slight out-of-plane vibrations of the phthalocyanine ligands.

The Raman spectra have been obtained and the temperature dependence of the conductivity of organic semiconductor structures based on butyl-substituted erbium monophthalocyanine and erbium triphthalocyanine has been studied. It has been found experimentally that the activation energy decreases dramatically and the Raman spectra exhibits four new peaks in the region of large Raman shifts as the molecular structure of the samples becomes more complicated.

Hitherto unknown phosphorus-containing 4,5-bis(diethoxyphosphorylmethyl)- and 4-methyl-5-diethoxyphosphorylmethylphthalonitriles were synthesized starting from o-xylene. Their tetramerization afforded free phthalocyanine ligands and their complexes with Zn, Ni, Co, and a number of rare-earth metals. The spectral and electrochemical properties of the phthalocyanines synthesized were studied.

New alkyl-substituted phosphorus phthalocyanines and triazatetrabenzocorroles were synthesized. The structures of these complexes were confirmed by 1H, 13C, and 31P NMR spectroscopy, mass spectrometry, and electronic absorption spectroscopy.