SPECTRAL-LUMINESCENT PROPERTIES OF MONODEPROTONATED FORMS OF HYDROPHYLIC CATIONIC PORPHYRINS AND STUDY OF THE POSSIBILITY TO FORM THEIR J-AGGREGATES

UDC 535.37+541.65+543.4

 

Shakel Anton Yur’evich – student. Belarusian State Technological University (13a, Sverdlova str., 220006, Minsk, Republic of Belarus). E-mail: a.shakel@mail.ru

Melnik Aliaksei Dzmitrievich – student. Belarusian State Technological University (13a, Sverdlova str., 220006, Minsk, Republic of Belarus). E-mail: alex.mel.am99@gmail.com

Kruk Mikalai Mikalaevich – DSc (Physics and Mathematics), Professor, Head of the Department of Physics. Belarusian State Technological University (13a, Sverdlova str., 220006, Minsk, Republic of Belarus). E-mail: m.kruk@belstu.by

DOI: https://doi.org/10.52065/2520-6141-2024-278-4.

 

Key words: porphyrine, peripheral substitution, deprotonation, fluorescence, J-aggregate, Coulomb interactions.

For citation: Shakel A. Yu., Melnik A. D., Kruk M. M. Spectral-luminescent properties of monodeprotonated forms of hydrophilic cationic porphyrins and study of the possibility to form their J-aggregates. Proceedings of BSTU, issue 3, Physics and Mathematics. Informatics, 2024, no. 1 (278), pp. 26–31 (In Russian). DOI: 10.52065/2520-6141-2024-278-4.

Abstract

In this work, the spectral and luminescent characteristics of monodeprotonated forms of two isomeric hydrophilic cationic porphyrins, 5,10,15,20-(4-N-methylpyridyl)-porphyrin and 5,10,15,20-(3-N-methylpyridyl)- porphyrin, have been studied. It was shown that the spectral and luminescent characteristics of two isomers differ significantly, and the difference is explained by different mechanisms of electronic communication between the macrocycle and the substituents. For a para-substituted derivative, both mesomeric and inductive effects are observed, leading to a shift in electron density from the molecular orbitals of the porphyrin to the substituents, while in the case of a meta-substituted derivative, the mesomeric effect is absent. The possibility of the formation of J-aggregates by these compounds with increasing concentration in solution was investigated. It has been established that, despite the fulfillment of the necessary requirement, which consists in the bipolar nature of the charge distribution in the monomer, J-aggregates are not formed. It is proposed that the stability of monodeprotonated monomers of the studied porphyrins against the aggregation is due to two factors: firstly, the positive charge in the peripheral substituents is delocalized throughout the fragment, which does not allow for point Coulomb interaction; secondly, the proton in the macrocycle core is also delocalized, and is located in the plane of the macrocycle, which increases the distance between interacting centers. As a result, the strength of the Coulomb interactions is insufficient to ensure binding.

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20.11.2023