Abstract
This paper presents the results of a systematic study aimed at searching for organometallic molecules with a large dipole moment in order to create new film electret materials. A number of porphyrin complexes of transition metals, titanium, and vanadium and also complexes with bismuth(iii) iodide with an axial metal—oxygen bond were synthesized. The obtained compounds were identified by physicochemical methods (IR spectroscopy and X-ray photoelectron spectroscopy). The optimized geometry of the complexes, their vibrational spectra, dipole moments, and charge density distributions were evaluated by quantum chemical calculations. The Mulliken population analysis was performed. The maximum dipole moments were found for BiI etioporphyrin II (6.47 D) and BiI 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin (3.87 D). The metal ion acts as a transmitter of electron density from nitrogen atoms to the counterion, resulting in an increase in the dipole moment of the molecule as a whole compared to the starting porphyrin ligands. The inclusion of porphyrin complexes under the action of an electric field resulted in the formation of polyvinyl acetate films. Copper layers 100 nm thick were deposited by magnetron sputtering onto both sides of these films. The dielectric properties and the temperature dependences of thermally stimulated depolarization currents of the obtained samples were studied. All samples were found to have a pronounced electret effect.
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We are grateful to the Head of the Ion-Plasma Technology Laboratory of the Ivanovo State University of Chemistry and Technology B. L. Gorberg for help in preparing samples using the MIR-2 magnetron sputtering system.
The study was financially supported by the Russian Foundation for Basic Research (Project No. 20-03-00244) and the Ministry of Science and Higher Education of the Russian Federation (Project Nos 0706-2020-0019 and FSFZ-2023-0004) using the equipment of the Center for Collective Use of the MIREA — Russian Technological University and the Center for Collective Use of the Ivanovo State University of Chemistry and Technology (with the financial support of the Ministry of Science and Higher Education of the Russian Federation, agreement No. 075-15-2021-671).
No human or animal subjects were used in this research.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, Vol. 72, No. 9, pp. 2070–2082, September, 2023.
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Ageeva, T.A., Bush, A.A., Golubev, D.V. et al. Porphyrin complexes of transition metals with a large dipole moment as active components of new film electret materials. Russ Chem Bull 72, 2070–2082 (2023). https://doi.org/10.1007/s11172-023-4001-0
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DOI: https://doi.org/10.1007/s11172-023-4001-0