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Spectral-Fluorescence Properties of Zn(II)-Octaphenyltetraazaporphyrins

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Abstract

Zn(II)-octa-(4-chlorophenyl)- and Zn(II)-octa-(4-bromophenyl)tetraazaporphyrins were synthesized by the reaction of cyclotetramerization of di-(4-chlorophenyl)- and di-(4-bromophenyl)maleonitriles with zinc(II) chloride. The obtained compounds were identified by UV-vis, IR, NMR 1H spectroscopy and mass spectrometry. Geometry optimization of the series of halogenated Zn(II)-octaaryltetraazaporphyrins was performed using the density functional method with the BP86 functional and the def2-TZVP basis set. An analysis of the distribution of molecular orbital energies in the neighborhood of highest occupied molecular orbitals (HOMO and HOMO-1) and lowest unoccupied molecular orbitals (LUMO and LUMO+1) and the width of the HOMO – LUMO energy gaps (EH-L) was performed for the studied compounds. Fluorimetric measurements of the Zn(II)-octaphenyltetraazaporphyrins in toluene were carried out and fluorescence quantum yields of studied compounds were determined and analyzed. It has been shown that the halogen on the para-position of the phenyl groups significantly affects the value of the obtained quantum yields of fluorescence emission but does not significantly affect the Stokes shifts.

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  • 18 May 2020

    The original version of this article unfortunately contained a mistake. In the section of ���Acknowledgements��� the grant number is incorrectly indicated. The corrected grant number is given below.

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Acknowledgements

This work was supported by the Russian Science Foundation (project number 19-73-200-79) and employed with the equipment of the Shared Facilities Center of the Institute of Organic Chemistry of the Russian Academy of Sciences.

The authors thank the Joint Supercomputer Center of the Russian Academy of Sciences (Moscow) for providing the resources of the MVS-100 K cluster.

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Authors and Affiliations

  1. G. A. Krestov Institute of Solution Chemistry of the Russian Academy of Sciences, Akademicheskaya Str. 1, Ivanovo, Russian Federation, 153045

    Olga A. Dmitrieva, Natalya V. Chizhova & Nugzar Z. Mamardashvili

  2. Ivanovo State University of Chemistry and Technology, Sheremetevskiy Av. 7, Ivanovo, Russian Federation, 153000

    Alexey I. Rusanov & Mikhail O. Koifman

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  1. Olga A. Dmitrieva
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Correspondence to Nugzar Z. Mamardashvili.

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Dmitrieva, O.A., Chizhova, N.V., Rusanov, A.I. et al. Spectral-Fluorescence Properties of Zn(II)-Octaphenyltetraazaporphyrins. J Fluoresc 30, 657–664 (2020). https://doi.org/10.1007/s10895-020-02530-1

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