Synthesis and Some Physical-Chemical Properties of meso-Aryl- and Alkyl Substituted Corroles and their Metal Complexes

Петрова, Д. В.; Семейкин, А. С.; Berezina, N. M.; Березин, М. Б.; Базанов, М. И.

doi:10.6060/mhc190553s

Cited by 11 publications

(5 citation statements)

References 26 publications

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“…The 2,3,7,13,17,18-hexamethyl-8,12-di-n-butylcorrole and10-(4,6-dichloropyrimi-dinyl)-5,15-dimesityl-corrole derivatives used in the study were prepared and purified according to the original synthetic procedures [20,21]. The working solutions were prepared by dissolving the corrole powder in organic solvents.…”

Section: Methodsmentioning

confidence: 99%

Absorption Spectra of Protonated Corroles: Two Distinct Patterns Due to Peripheral Substitution Architecture

Gladkov,

Klenitsky,

Kruk

2023

Organics

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The origin of individual features in the ground state absorption spectra of two protonated corroles differing in the architecture of peripheral substitution (either Cm-aryl or Cb-alkyl) have been studied in detail with the ground state absorption spectroscopy and density functional theory calculations. The geometry optimization, molecular orbitals and absorption spectra calculation have been carried out. It was found that protonation leads to the saddle type macrocycle conformation in contrast with the wave type conformation known for the parent-free base corroles. The mean plane deviation parameter Δ23 for the macrocycle, pyrrole tilting angles and the degree of pyramidalization λ2 of all four pyrrole nitrogens was found to depend on the peripheral substitution architecture. Macrocycle conformation of the protonated forms has distinct asymmetrical features which are reflected by the sets of values of the tilting angles and values of pyramidalization degree. The pair of pyrroles B and C has smaller tilting angles and higher pyramidalization degree values, whereas the opposite trend was found for the pair of pyrroles A and D. Electronic effects and structural differences induced by substitution lead to the pronounced shifts of the molecular orbitals. In the Cb-alkylated corrole, almost-degenerated HOMO and HOMO-1 molecular orbitals lead to enhancement of the configuration interaction. As a result, the Qx transition oscillator strength goes down, becoming comparable to that of the Qy one. A large HOMO-HUMO-1gap in the Cm-aryl corrole minimizes the configuration interaction, giving rise to Qx band domination in the visible range spectrum.

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Section: Methodsmentioning

confidence: 99%

Absorption Spectra of Protonated Corroles: Two Distinct Patterns Due to Peripheral Substitution Architecture

Gladkov,

Klenitsky,

Kruk

2023

Organics

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“…В качестве объектов исследования выбраны свободные основания НзПМезгК и НзОАлкК, представляющие собой молекулы-архетипы для двух типов периферического замещения макроцикла, содержащие соответственно заместители в Ст-положениях макроцикла (как правило, арильные группы) и в Соположениях макроцикла (чаще всего алкильные группы). Соединения синтезированы по методикам [23,24].…”

unclassified

“…Измерения проведены в кварцевых кюветах 1x1 см производства фирмы Hellma, которые помещали в термостатированное кюветное отделение спектрофлуорометра. Концентрация корролов в растворах <5 • 10-6 М определялась спектрофотометрически с использованием коэффициентов экстинкции [23,24].…”

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Solvatochromism of the Free Base Corroles

Kruk

2022

Ž. prikl. spektrosk. (Minsk)

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For two free base corroles with different architecture of peripheral substitution, the solvatochromic shifts of absorption bands in a series of solvents of different nature are herein determined, and the nature of the solvatochromic effects is analyzed by the Valentine method. It is found that the solvatochromism of the free bases of corroles originates due to universal nonspecific interactions, and the short-wavelength T2 tautomer experiences stronger solvation. It is shown that in polar aprotic solvents (acetone, acetonitrile, dimethylformamide, and dimethylsulfoxide), specific acid-base interactions occur simultaneously, leading to the formation of the deprotonated form. It is found that both deprotonated and protonated forms of corroles also show nonspecific solvation, leading to solvatochromic shifts, the magnitude of which exceeds that for free base corroles. It is proposed that this feature is due to an excess (negative or positive) electronic charge of the macrocycle.

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“…Молекулы НзТАлкК и НзОАлкК синтезированы по методике [12] и исследованы методами кван товой химии и молекулярной спектроскопии, в то время как незамещенный коррол НзК исследован только теоретически, поскольку до настоящего времени все попытки синтеза молекулы свободного основания коррола без периферических заместителей успеха не имели. Для незамещенного коррола указаны нумерация атомов макроцикла согласно номенклатуре ШРАС и обозначения пиррольных колец.…”

unclassified

“…Для измерения электронных спектров поглощения соединения растворяли в дихлорметане (Aldrich, spectroscopic grade). Спектры регистрировали на спектрофлуорометре СМ2203 ("Солар", Беларусь) при концентрациях растворенных соединений ~1 • КГ6 М, которые определяли спектрофо тометрическим методом с использованием известных коэффициентов экстинкции [12]. Растворы по…”

unclassified

QUANTUM-CHEMICAL CALCULATION AND SPECTROSCOPIC STUDY OF Π-Conjugation PATHWAY IN NH-TAUTOMERS OF THE FREE BASE CORROLES

Klenitsky

Гладков

Vershilovskaya

et al. 2021

Ž. prikl. spektrosk. (Minsk)

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The π-conjugation pathway was identified and the degree of aromaticity for the NH-tautomers of the free base corroles was determined by quantum chemistry methods and absorption spectroscopy. Different participation of the macrocycle skeletal atoms in formation of the π-conjugation pathway was established, and it was supposed that conjugation pathway consisting of 18 π-electrons were dominating. At the same time, each of two NH-tautomers possesses its own distinct π-conjugation pathway, which provides the differences in the aromaticity degree. It was shown that architecture of the peripheral substitution of a macrocycle influences the degree of aromaticity. Method of the control over the equilibrium between two NH-tautomers was proposed and experimentally proved. It consists in the design of the electronic density distribution in macrocycle which is characteristic for one of the tautomers.

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Synthesis and Some Physical-Chemical Properties of meso-Aryl- and Alkyl Substituted Corroles and their Metal Complexes

Cited by 11 publications

References 26 publications

Absorption Spectra of Protonated Corroles: Two Distinct Patterns Due to Peripheral Substitution Architecture

Absorption Spectra of Protonated Corroles: Two Distinct Patterns Due to Peripheral Substitution Architecture

Solvatochromism of the Free Base Corroles

QUANTUM-CHEMICAL CALCULATION AND SPECTROSCOPIC STUDY OF Π-Conjugation PATHWAY IN NH-TAUTOMERS OF THE FREE BASE CORROLES

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