Coordination reaction of manganese(III)porphyrins with pyridine as model to obtain the donor-acceptor dyads with fullerene acceptors

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Аннотация

In connection with the use of the pyridyl group as the bridge in the coordination of metalloporphyrins with fullerene acceptors to obtain the photoinduced electron transfer donor-acceptor systems, the study of coordination of unsubstituted pyridine molecules and the determination of the chemical structure, spectral properties, and stability of the obtained complexes becomes relevant. The coordination of pyridine molecules by manganese(III)porphyrins depending on their structure was studied in this work. In all cases, coordination ends with the formation of 1 : 1 complexes in toluene, the structure of which was established using the data of MALDI-TOF mass spectrometry and 1H NMR spectroscopy. The numerical values of the stability constants of the coordination complexes were determined; they change from 0.16 to 104 L/mol depending on the nature of the axial anion in the manganese(III)porphyrin, the structure of the tetrapyrrole macrocycle, and the functional substitution in it. The obtained data facilitate the choice of structures in the creation of hybrid materials based on metalloporphyrins by the immobilization and supramolecular chemistry methods.

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Авторлар туралы

E. Ovchenkova

Krestov Institute of Solution Chemistry of the Russian Academy of Sciences

Хат алмасуға жауапты Автор.
Email: enk@isc-ras.ru
Ресей, Ivanovo 153045

A. Elkhovikova

Ivanovo State University of Chemical Technology

Email: enk@isc-ras.ru
Ресей, Ivanovo, 153000

T. Lomova

Krestov Institute of Solution Chemistry of the Russian Academy of Sciences

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

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2. Fig. 1. Structural formulas and electronic spectra in toluene (AcO)MnTPP/(AcO)MnTtBuPP (1) and (AcO)MnTAP(4-tBuPh)8 (2).

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3. Fig. 2. Change in ESP in toluene (AcO)MnTtBuPP (a) and (AcO)MnTAP(4-tBuPh)8 (b) with the development of Py from 0 to 10 mol/l.

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4. Fig. 3. Dependences of log I on log CPy for the mode (AcO)MnTPP (1, tg = 1.03, R2 = 0.98), (AcO)MnTtBuPP (2, tg = 1.03, R2 = 0.98 ) and (AcO)MnTAP(4 -tBuPh)8 (3, tan = 0.96, R2 = 0.99) with Py in toluene at 298 K.

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5. Fig. 4. MALDI-TOF mass spectrum of (AcO)(Py)MnTPP.

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6. Fig. 5. 1H NMR spectra of (AcO)MnTtBuPP (a) and (AcO)(Py)MnTtBuPP (b) in CDCl3.

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