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. 2025 May 14;15(1):16668.
doi: 10.1038/s41598-025-00428-1.

Pyrrole dicarboxylate substituted porphyrazine, microwave assisted synthesis and properties

Wojciech Szczolko  1 , Michal Kryjewski  2 , Tomasz Koczorowski  3 , Eunice Zuchowska  3 , Lukasz Popenda  4 , Dariusz T Mlynarczyk  3
Affiliations

Pyrrole dicarboxylate substituted porphyrazine, microwave assisted synthesis and properties

Wojciech Szczolko et al. Sci Rep. .

Abstract

In this study, a new magnesium(II) porphyrazine derivative tetrasubstituted with dicarboxypyrrolyl moieties was synthesized. Two different approaches were used, utilizing conventional heating and microwave irradiation. The developed three-step processes were compared showing the superior performance of the microwave-assisted organic synthesis. The new macrocycle and the novel maleonitrile derivatives were characterized using spectral techniques (mass spectrometry, NMR spectroscopy, UV-Vis spectrophotometry) and the ability of the porphyrazine to generate singlet oxygen assessed using the method with 1,3-diphenylisobenzofuran. The singlet oxygen generation quantum yields were found to be moderate (ΦΔ = 0.23 and 0.22 in DMF and DMSO, respectively) and no aggregation behavior was noted in a series of dilutions. Additionally, the acute toxicity test using Microtox was performed showing almost no toxicity at the concentration of 10- 5 mol/L. The electrochemical studies revealed three redox processes of targeted porphyrazine with low first oxidation peak, whereas the spectroelectrochemistry showed the formation of both cationic and anionic species at proper potentials.

Keywords: Diaminomaleonitrile; Electrochemistry, aminoporphyrazines; Microwave-assisted organic synthesis; Porphyrazine; Singlet oxygen.

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Conflict of interest statement

Competing interests: The authors declare no competing interests.

Figures

Fig. 1
Fig. 1
Synthetic pathway leading to porphyrazine 4. Conditions and reagents: classical synthesis: (i) methanol, reflux, 24 h; (ii) NaH, THF, (CH3O)2SO2, − 17 °C to room temperature; (iii) magnesium(II) butoxide, n-butanol, reflux, 20 h; microwave-assisted organic synthesis: (i) methanol, 120 °C, 10 min; (ii) MeI, Cs2CO3, THF, 120 °C, 20 min; (iii) magnesium(II) butoxide, n-butanol, 180 °C, 8 min.
Fig. 2
Fig. 2
The structure of Pz 4, with NMR chemical shifts in ppm (italic font indicates carbon chemical shifts). The arrows indicate correlations observed in the 1H-13C HMBC spectrum.
Fig. 3
Fig. 3
CV and DPV voltammograms of 4 at different scan rates in 0.1 M TBAP/DCM. DPV parameters: modulation amplitude 20 mV, step rate 10 mV/s.
Fig. 4
Fig. 4
UV-Vis spectra of 4 in 0.1 M TBAP/DCM at Eapp= 0.73 V (left), Eapp = − 1.35 V (right). Red spectra were recorded without potential, whereas the blue ones appeared after 120 s of proper potential was applied.
Fig. 5
Fig. 5
UV-Vis spectra of 4 in (a) DMF and (b) DMSO at different concentrations (left), and correlation between concentration and absorbance at wavelength corresponding to the absorption peaks (right).
Fig. 6
Fig. 6
Absorption, emission and excitation spectra of Pz 4 in (a) DMF and (b) DMSO.
Fig. 7
Fig. 7
Changes in the UV-Vis spectrum, corresponding to different irradiation times for the mixture of 4 and DPBF in DMF (a) and DMSO (b).
Fig. 8
Fig. 8
The changes in A. fischeri bioluminescence as a function of Pz 4 concentration.
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References

    1. Stuzhin, P. A. & Ercolani, C. Porphyrazines with annulated heterocycles. in The Porphyrin Handbook 263–364 (Elsevier, 10.1016/B978-0-08-092389-5.50011-0. (2003).
    1. Fuchter, M. J. et al. ROM Polymerization-Capture-Release strategy for the Chromatography-Free synthesis of novel unsymmetrical porphyrazines. J. Org. Chem.70, 2793–2802 (2005). - PubMed
    1. Mani, N. S. et al. Synthesis and characterisation of porphyrazinoctamine derivatives: X-ray crystallographic studies of [2,3,7,8,12,13,17,18-octakis(dibenzylamino)- porphyrazinato]magnesium(II) and {2,3,7,8,12,13,17,18-octakis[allyl(benzyl)amino]- porphyrazinato} nickel(II). J. Chem. Soc., Chem. Commun. (1994) (2095). 10.1039/c39940002095
    1. Fuchter, M. J. et al. Synthesis of porphyrazine-octaamine, hexamine and Diamine derivatives. Tetrahedron61, 6115–6130 (2005).
    1. Leng, F., Wang, X., Jin, L. & Yin, B. The synthesis and properties of unsymmetrical porphyrazines annulated with a tetrathiafulvalene bearing two tetraethylene glycol units. Dyes Pigm.87, 89–94 (2010).

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