Synthesis and spectroscopic characterization of Ru(II) and Sn(IV)-porphyrins supramolecular complexes

Khodov, Ilya A.; Nikiforov, M. Yu.; Al'per, G. A.; Мамардашвили, Г. М.; Мамардашвили, Н. Ж.; Койфман, О. И.

doi:10.1016/j.molstruc.2014.10.070

Cited by 29 publications

(9 citation statements)

References 25 publications

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“…Supramolecular self-organization of simple porphyrin assemblies resulted mostly in linear structures involving axial coordination of the metal sites via bidentate ligands. [53] However, the structural parameters of such assemblies have been rarely published. Here, we used unfunctionalized tetramesitylporphyrin ligand which can be readily available.…”

Section: Discussionmentioning

confidence: 99%

Supramolecular Iron(III) Tetramesitylporphyrin Cluster Structure Assembled by Hydrogen Bonding with Sulfuric Acid

Kudrik¹,

Нефедов²,

Sorokin³

2019

MHC

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We present here the first crystalline assembly of a supramolecular structure formed by iron(III) 5,10,15,20-tetrakismesitylporphyrin via hydrogen bonding with charge compensating hydrosulfate residues. Two additional molecules of sulfuric acid provide hydrogen bonding connection of four iron porphyrin units to form a fragment with interporphyrin void where two iron sites are situated at 9.52 Å distance. The insertion of two molecules of sulfuric acid into cavity formed by four Fe(III) porphyrin molecules led to the formation of the cluster structure with dihedral angle of 53.3° between adjacent porphyrin molecules Fe(1A)N 4 /Fe(2A)N 4 and parallel Fe(1A)N 4 /Fe(1B)N 4 and Fe(2A)N 4 /Fe(2B)N 4 planes. Such a supramolecular material, where four iron sites in the porphyrin ligand environment are strongly connected via network of the hydrogen bonds provides a new tool for exploring different applications involving multielectronic processes.

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Section: Discussionmentioning

confidence: 99%

Supramolecular Iron(III) Tetramesitylporphyrin Cluster Structure Assembled by Hydrogen Bonding with Sulfuric Acid

Kudrik¹,

Нефедов²,

Sorokin³

2019

MHC

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“…The lengths of the formed hydrogen bond and the energies of the intermolecular interaction of the bis-axial complex are in good agreement with the values of the energies of hydrogen bonds determined from the formation constants of the Co(III)P-(L)(H2O) complexes ( Figure 5). For the analysis of the chemical structure of Со(III)P(1-2)and its complexes with L1-L3, 1 H NMR spectrawere obtained as shown in the Figure 4, which are thesuperposition (convolution) of spectra, relating to a certainrange of self-diffusion coefficients, which thesebonds are characterized [17,[27][28][29][30][31]. Such superposition is obtainedby a projection of a pseudo-two-dimensional spectrum ofthe diffusive ordered DOSY spectroscopy on the set rangeof self-diffusion coefficients.…”

Section: Co(iii)p and Lmentioning

confidence: 99%

Molecular Recognition of Imidazole Derivatives by Co(III)-Porphyrins in Phosphate Buffer (pH = 7.4) and Cetylpyridinium Chloride Containing Solutions

et al. 2021

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Bymeans of spectrophotometric titration and NMR spectroscopy, the selective binding ability ofthe Co(III)-5,15-bis-(3-hydroxyphenyl)-10,20-bis-(4-sulfophenyl)porphyrin (Со(III)Р1) andCo(III)-5,15-bis-(2-hydroxyphenyl)-10,20-bis-(4-sulfophenyl)porphyrin (Со(III)Р2) towards imidazole derivatives of various nature (imidazole (L1), metronidazole (L2), and histamine (L3)) in phosphate buffer (pH 7.4) has been studied. It was found that in the case of L2, L3 the binding of the “first” ligand molecule by porphyrinatesCo(III)P1 and Co(III)P2 occurs with the formation of complexes with two binding sites (donor–acceptor bond at the center and hydrogen bond at the periphery of the macrocycle), while the “second” ligand molecule is added to the metalloporphyrin only due to the formation of the donor–acceptor bond at the macrocycle coordination center. The formation of stable complexes with two binding sites has been confirmed by density functional theory method (DFT) quantum chemical calculations and two-dimensional NMR experiments. It was shown that among the studied porphyrinates, Co(III)P2 is more selective towards to L1-L3 ligands, and localization of cobalt porphyrinates in cetylpyridinium chloride (CPC) micelles does not prevent the studied imidazole derivatives reversible binding. The obtained materials can be used to develop effective receptors for recognition, delivery, and prolonged release of drug compounds to the sites of their functioning. Considering that cetylpyridinium chloride is a widely used cationic biocide as a disinfectant, the designed materials may also prove to be effective antimicrobial agents.

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“…), [1][2][3] а так же при реализации рецепторной [4,5] и органокаталитической [5,6] функций порфиринов и их аналогов. Метод DOSY интенсивно используется для изучения химических свойств порфиринов и их аналогов, [7][8][9][10][11][12][13][14][15] в том числе процессов протонного обмена с участием внутрициклических протонов NH. [12][13][14][15] Ранее нами было показано, что обменные процессы с участием внутрициклических групп NH синтетических и природных порфиринов с молекулами воды, содержащейся в CDCl 3 и C 6 D 6 , проявляются в DOSY увеличением коэффициентов самодиффузии D протонов NH (D NH ) по сравнению с протонами С-Н (D СH ) порфириновой молекулы, причем разница D NH и D СH зависит от того, насколько интенсивно внутрициклическая группа NH участвует в обменных процессах.…”

Section: Introductionunclassified

Activation Energy of Proton Exchange Processes of Deuteroporphyrin IX Dimethyl Ester with Water in C6D6 Medium Based on DOSY Data

Stolypko¹,

Белых²

2019

MHC

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Методом DOSY определены энергии активации процессов, обуславливающих изменение коэффициента самодиффузии D протонов воды и внутрициклических протонов NH диметилового эфира дейтеропорфирина IX (D W и D NH ), связанных с протонным обменом между молекулами этих соединений в среде C 6 D 6 . Энергия активации процессов, обуславливающих изменение D W и D NH , составила соответственно Е а (W) = 27.3 ± 1.3 кДж/моль и Е а (NH) = 15.8 ± 0.7 кДж/моль. Судя по полученным данным, активационные барьеры во всех случаях связаны с разрывом водородных связей при образовании и разрушении ассоциатов порфирин-вода, формирование которых является необходимым условием протекания обмена.Ключевые слова: Порфирины, спектроскопия DOSY, протонный обмен, энергия активации, дейтеропорфирин IX. The activation energies of the processes which determine the change in the self-diffusion coefficient D of water protons and the internal NH protons of deuteroporphyrin IX dimethyl ester (D W and D NH ) associated with the proton exchangebetween the molecules of these compounds in C 6 D 6 medium are determined by the DOSY method. The activation energies of the processes that cause the change in D W and D NH were estimated to be E a (W) = 27.3 ± 1.3 kJ/mol and E a (NH) = 15.8 ± 0.7 kJ/mol, respectively. The data obtained show, that activation barriers in all cases are associated with the breaking of hydrogen bonds during the formation and destruction of porphyrin-water associates, the formation of which is a necessary condition for the exchange.

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Synthesis and spectroscopic characterization of Ru(II) and Sn(IV)-porphyrins supramolecular complexes

Cited by 29 publications

References 25 publications

Supramolecular Iron(III) Tetramesitylporphyrin Cluster Structure Assembled by Hydrogen Bonding with Sulfuric Acid

Supramolecular Iron(III) Tetramesitylporphyrin Cluster Structure Assembled by Hydrogen Bonding with Sulfuric Acid

Molecular Recognition of Imidazole Derivatives by Co(III)-Porphyrins in Phosphate Buffer (pH = 7.4) and Cetylpyridinium Chloride Containing Solutions

Activation Energy of Proton Exchange Processes of Deuteroporphyrin IX Dimethyl Ester with Water in C6D6 Medium Based on DOSY Data

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