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1

Mix-substituted phthalocyanines of a “push–pull”-type and their metal complexes as prospective nanostructured materials for optoelectronics

Usol'tseva N. V., Smirnova A. I., Kazak A. V., Giricheva N. I., Galanin N. E., Shaposhnikov G. P., Bodnarchuk V. V., Yablonskii S. V.

Opto-Electronics Review

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2017

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Vol. 25, No. 2

127--136

EN

To study the influence of structural features of phthalocyanine (Pc) derivatives on their physico-chemical properties in bulk and thin films, 23 new phthalocyanines with different quantity and ratio of donor (alkyloxy-groups, in fragment “A”) and acceptor (Cl-, in fragment “B”) substituents in one molecule of the A3B, ABAB and AABB types with varied length of alkyloxy-substituents and their metal complexes were designed and synthesized. A comparative analysis of spectral, mesomorphic and photoelectric properties of these mix-substituted phthalocyanines of a “push–pull” type was performed. It was shown that non-peripheral substitution by alkyloxy-fragments in hetero-substituted Pcs (similar to homo-substituted Pc) leads to red-shifting of the Q-band into near-IR region. The intensity of photoluminescence, position of peaks and their splitting are strongly connected with chemical structure of Pcs and the type of solvent. In contrast to non-mesogenic octyloxy-Pc (A4) having alkyloxy-substituents in non-peripheral positions, 22 of 23 synthesized compounds possess columnar mesomorphism. The change of donor–acceptor ratio can influence the type of mesophase. A new approach to the creation of materials for optoelectronics is proposed and implemented, which includes design of compounds possessing vitrification from mesophase with maintenance of a columnar order, absorption in the near IR-region of the spectrum and good performance electrophysical characteristics simultaneously.

2

Synthesis, Crystal Structure, Characterization and Ab Initio Calculations on a Dicycle Pyrazoline Derivative

Guo H. M., Zhang J., Zhao P. S., Jian F. F.

Polish Journal of Chemistry

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2009

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Vol. 83, nr 2

263-274

EN

A dicycle pyrazoline derivative, 1-acetyl-5-(2-chlorophenyl)-3,4-(a-o-chlorotolylene-cyclohexano) pyrazoline, was synthesized and characterized by elemental analysis, IR, UV-Vis, fluorescence spectra and X-ray single crystal diffraction. Quantum chemical calculations were performed by using B3LYP and HF methods with 6-311G* basis set. Both methods can well simulate the molecular structure. Vibrational frequencies were predicted, assigned and compared with the experimental values, which suggest that both methods can only approximatively predict the vibrational frequencies. Electronic absorption spectra predicted by B3LYP/6-311G asterisk operator method well corresponding with the experimental data and natural bond orbital analyses indicate that the absorption bands are mainly derived from the contribution of n → pi asterisk operator and pi → pi asterisk operator transitions. For the system studied here, HF/6-311G asterisk operator method cannot be used to obtain the electronic absorption spectra. On the basis of vibrational analysis, the thermodynamic properties of the title compound at different temperature have been calculated, revealing the correlations between C0 p,m S 0 m, H0 m and temperature.

3

Synthesis, Characterization, Crystal Structure and Quantum Chemical Studies on N-Dimethyl-N'-phenyl-thiocarbamide

Zhao P. S., Qin Y. Q., Zhang J., Jian F. F.

Polish Journal of Chemistry

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2008

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Vol. 82, nr 11

2153-2165

EN

The title compound of N-dimethyl-Nc-phenyl-thiocarbamide was synthesized and characterized by elemental analysis, IR, NMR, electronic spectra and X-ray single crystal diffraction. Quantum chemical calculations were performed by using B3LYP and HF methods with 6-311G** basis set. Both the methods well simulate the molecular structure. Vibrational frequencies were predicted, assigned and compared with the experimental values, which suggest that both methods can only predict the vibrational frequencies approximatively. The nuclear magnetic shieldings were predicted by using GIAO method and compared with experiment. The results show that, for the title compound, B3LYP/6-311G** method better predicts the 13C NMR spectra than HF/6-311G**, whereas HF/6-311G** better predicts the 1H NMR spectra than B3LYP/6-311G**. Electronic absorption spectra predicted by B3LYP/6-311G** method are closer to the experimental data and natural bond orbital analyses indicate that the absorption bands are mainly from the contribution of n → pi* and pi → pi* transitions. For the system studied here, HF/6-311G** method can not be used to obtain the electronic absorption spectra. On the basis of vibrational analyses, the thermodynamic properties of the title compound at different temperatures have been calculated, revealing the correlations between Cp,m 0 , Sm 0 , Hm 0 and temperatures.

4

Synthesis, Characterization and ab initio Calculations on 1-Phenyl-3-p-fluorophenyl-5-p-methoxyphenyl-2-pyrazoline

Zhao P. S., Li Y. F., Guo H. M., Wang X., Jian F. F.

Polish Journal of Chemistry

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2007

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Vol. 81, nr 10

1735-1735

EN

1-Phenyl-3-p-fluorophenyl-5-p-methoxyphenyl-2-pyrazoline has been synthesized and characterized by elemental analysis, IR, UV-Vis and X-ray single crystal diffraction. Ab initio calculations for the title compound have been carried out and the calculated results show that HF/6-311G** method can well reproduce the structural parameters. The theoretical electronic absorption spectra have been predicted by using 6-311G** and 6-311++G** basis sets and compared with the experimental values, indicating that HF-CIS method can well predict electronic absorption spectra for the system studied here. On the basis of vibrational analyses, the thermodynamic properties of the title compound at different temperatures have been calculated, revealing the correlations between C 0 p,m , S 0 m , H 0 m and temperature.

5

Experimental and Theoretical Study on 3-Benzyl-4-phenyl-1,2,4-triazole-5-thione

Zhao P., Li R., Xu J., Zhang W.

Polish Journal of Chemistry

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2007

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Vol. 81, nr 8

1495-1503

EN

The 3-benzyl-4-phenyl-1,2,4-triazole-5-thione was synthesized and examined by elementary analysis, IR and electronic spectra. Density functional theory calculations of the structure, natural bond orbitals and thermodynamic functions of the title compound were performed at B3LYP/6-311G** level of theory. Vibrational frequencies were predicted, assigned and compared with the experimental data, and they are supported by the experimental data. Electronic absorption spectrawere calculated by the time-dependent density functional theory (TD-DFT), which indicates that the two absorption bands are mainly derived from the contribution of bands *. The calculation of the second order optical nonlinearity was carried out, giving value of molecular hyperpolarizability equal to 4.025ź10–30 esu. These calculated results were also compared with results obtained for a similar molecule, 4-phenyl-3-[(1,2,4-triazol-1-yl)methyl]-triazole-5-thione, reported earlier by this group.

6

Experimental and Theoretical Study on4-Phenyl-3-[(1,2,4-triazol-1-yl)methyl]-triazole-5-thione

Jian F., Zhao P., Bai Z., Cai Z.

Polish Journal of Chemistry

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2006

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Vol. 80, nr 2

325-333

EN

The title compound, 4-phenyl-3-[(1,2,4-triazol-1-yl)methyl]-triazole-5-thione, was synthesized and characterized by elemental analysis, IR and electronic spectra. Density functional theory calculations of the structure, natural bond orbital and thermodynamic functions of the title compound were performed at B3LYP/6-311G** level of theory. Vibrational frequencies were predicted, assigned, compared with the experimental values, and they are supported each other. Electronic absorption spectra were calculated by the time-dependent density functional theory (TD-DFT), which indicates that the two absorption bands aremainly derived from the contribution of bands pi--pi*. The calculation of the second order optical nonlinearity was carried out with PM3 semi-empirical method that resulted in the molecular hyperpolarizability equal to 4.397x10-30 esu.

7

Coordination States and Apparent Molar Volumes of Cobalt(II) Perchlorate and Cobalt(II) Chloride in N, N'-Diethylacetamide Solutions at 25 graduate C

Lipski P., Pastewski R., Grzybkowski W.

Polish Journal of Chemistry

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2005

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Vol. 79 / nr 9

1445-1459

EN

Visible absorption spectra and apparent molar volumes for CoCl2 and Co(ClO4)2 in N,N-diethylacetamide (DEA) as well as the spectra for the Co(ClO4)2 - CoCl2 - DEAand CoCl2- LiCl - DEA systems were studied. The results indicate formation of the electrically neutral CoCl2(DEA)2 complex, being the predominating chloro-complex of cobalt(II) in the solutions of CoCl2 in DEA. The formation constants of the consecutive chloro-complexes of cobalt(II) have been determined: logK1 = 5.28(+-0.10), logK2 =+ - 6.10(_0.08), logK3 = 3.31(+ - 0.05) and logK4 = 0.74(+ - 0.05).

8

Crystal Structure and Ab Initio Studies on (p-Methoxyphenyl)thiosemicarbazide

Zhao P., Jian F., Hou Y.

Polish Journal of Chemistry

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2004

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Vol. 78 / nr 10

1945-1951

EN

(p-Methoxyphenyl)thiosemicarbazide [CH3OC6H4NHNHCSNH2] has been prepared and characterized by elemental analysis, IR, electronic absorption spectra and X-ray single crystal diffraction. In the crystal lattice, there exist some intermolecular hydrogen bonds, _-_ stacking interactions and C-Hźźź_ supramolecule interactions, which stabilize the crystal structure. Ab initio calculations at HF/6-31G* level of the structure, charges distribution, electronic spectra, natural population analysis and thermodynamic properties at different temperatures have been performed. The calculated results show that the sulfur atom and nitrogen atoms have bigger negative charges, which result in they are the potential sites to react with the metallic ions. The electronic transitions associated with the electronic absorption spectra are mainly derived from the contribution of bands pi-pi*.