Influence of the Nature of the Central Atom on the Basicity of Octa(3,5-di-tert-butylphenoxy)phthalocyanine Complexes

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Abstract

The knowledge of the parameters and mechanisms of proton transfer from the medium to the macrocyclic ligand of highly substituted phthalocyanines complexes is necessary for the optimization of the technological processes of catalysis and creating functional materials. The complexes of octakis(3,5-di-tert-butylphenoxy)phthalocyanine with 3d-metal ions were synthesized and their acid-base reactions were studied using UV-vis and 1H NMR spectroscopy. The chemical structure of the complexes was established using elemental analysis, MALDI-TOF mass spectrometry, IR, 1H NMR and UV-vis spectroscopy. The complete protonation of Co, Ni and Cu complexes occurs in mixtures of dichloromethane – trifluoroacetic acid. The doubly and quadruple protonated forms are identified in the UV-vis spectra. The concentration ranges of existence, UV-vis parameters and thermodynamic stability constants of protonated forms were determined, as well as their relationship with the electronic structure of the coordination center.

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About the authors

E. N. Ovchenkova

Krestov Institute of Solution Chemistry of the Russian Academy of Sciences

Author for correspondence.
Email: enk@isc-ras.ru
Russian Federation, Ivanovo, 153045

T. N. Lomova

Krestov Institute of Solution Chemistry of the Russian Academy of Sciences

Email: enk@isc-ras.ru
Russian Federation, Ivanovo, 153045

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Supplementary files

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2. Fig. 1. Structural formula of metallophthalocyanines.

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3. Fig. 2. Variation of the electronic absorption spectrum of CuPc(3,5-di-tBuPh)8 in mixed solvent CF3COOH-CH2Cl2: CCF3COOH = 0-0.47 (a), 0.47-6.7 mol/L (b). The remaining lines correspond to intermediate acid concentrations.

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4. Fig. 3. Dependence of the logarithm of the indicator ratio on the acidity function H0 of the mixed solvent for CuPc(3,5-di-tBuPh)8 (1), CoPc(3,5-di-tBuPh)8 (2) and NiPc(3,5-di-tBuPh)8 (3) for the first (a) and second (b) protonation stages (R2 = 0.98-0.99).

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5. Fig. 4. Electronic absorption spectra of the protonated forms of CoPc(3,5-di-tBuPh)8 (a) and NiPc(3,5-di-tBuPh)8 (b) in CF3COOH-CH2Cl2.

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6. Fig. 5. 1H NMR spectrum of NiPc(3,5-di-tBuPh)8 (7.8 × 10-3 mol/L) in CDCl3 (a) and in CDCl3 supplemented with 0.36 (b), 1.6 (c) and 2.9 mol/L CF3COOH (d)

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