Electronic and steric effects controlling monomer–dimer self-assembly in 6<i>H</i>-1,4-diazepinoporphyrazines: an experimental and theoretical study

Tarakanov, Pavel A.; Simakov, Anton O.; Pushkarev, Victor E.; Конев, Д. В.; Goncharova, O. A.; Slesarenko, Nikita A.; Tarakanova, Ekaterina N.; Nefedov, Sergey E.; Stuzhin, Pavel A.

doi:10.1039/d2dt03371b

Cited by 3 publications

(3 citation statements)

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“…The 6 H ‐1,4‐diazepine ring contains diastereotopic axial and equatorial protons of the methylene 6‐CH 2 group which can give either a single resonance or two doublets if the inversion of the ring is slowed [32] . Indeed, for octaaryl‐substituted tetra(6 H ‐1,4‐diazepino)porphyrazines having a non‐flexible 1,4‐diazepine ring, two doublets at ~4.5–5.0 and ~5.5–6.0 ppm with the geminal splitting ( 2 J~11–12 Hz) are observed even at ambient and elevated temperatures [31,42] . In the case of octa‐ tert ‐butyl‐substituted derivatives for which inversion of the 1,4‐diazepine ring is fast on the NMR time scale, a single signal at ~3.5–4.0 ppm appears at elevated temperature [43] .…”

Section: Resultsmentioning

confidence: 99%

“…[32] Indeed, for octaaryl-substituted tetra(6H-1,4-diazepino)porphyrazines having a non-flexible 1,4-diazepine ring, two doublets at ~4.5-5.0 and ~5.5-6.0 ppm with the geminal splitting ( 2 J~11-12 Hz) are observed even at ambient and elevated temperatures. [31,42] In the case of octa-tert-butyl-substituted derivatives for which inversion of the 1,4-diazepine ring is fast on the NMR time scale, a single signal at ~3.5-4.0 ppm appears at elevated temperature. [43] In both cases the resonance of the carbon atom of the CH 2 group in tetra(6H-1,4diazepino)porphyrazines is observed at 35-45 ppm [42] similarly to its position in 2,4-diphenyl-3H-1,5benzodiazepine.…”

Section: Synthesis and Characterizationmentioning

confidence: 99%

“…[31,42] In the case of octa-tert-butyl-substituted derivatives for which inversion of the 1,4-diazepine ring is fast on the NMR time scale, a single signal at ~3.5-4.0 ppm appears at elevated temperature. [43] In both cases the resonance of the carbon atom of the CH 2 group in tetra(6H-1,4diazepino)porphyrazines is observed at 35-45 ppm [42] similarly to its position in 2,4-diphenyl-3H-1,5benzodiazepine. [44] In the subporphyrazine from the 2 nd fraction the carbon atom in the 6-position is bonded only with one proton, and the downfield shift of its resonance to 65.58 ppm in the 13 C NMR spectrum indicates the presence of an electronegative neighboring atom.…”

Section: Synthesis and Characterizationmentioning

confidence: 99%

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First Subphthalocyanine Analogue with Fused 6H‐1,4‐diazepine Ring and its Conversion to Aminobenzamide Derivative

Skvortsov,

Chufarin,

Zaitsev

et al. 2023

Asian J Org Chem

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Mixed cyclization of 5,7‐diphenyl‐6H‐1,4‐diazepine 2,3‐dicarbonitrile and tetrafluorophthalonitrile in the presence of boron trichloride affords along with symmetrical perfluorinated subphthakocyanine, [F12sPc], two novel subporphyrazine‐type products which were isolated by column chromatography and characterized by mass‐sprectometry, NMR, IR, UV‐VIS and fluorescent spectroscopy. It was established that co‐cyclomerization of dinitriles is accompanied by electrophilic chlorination of 1,4‐diazepine ring by evolved Cl2 resulting in formation of dibenzosubporphyrazine [F8sPc1] with fused 6‐chloro‐5,7‐diphenyl‐6H‐1,4‐diazepine fragment. According to DFT modelling and 1H NMR data, a more stable diastereomer with an axial Cl atom is formed and no inversion of the 1,4‐diazepine ring is observed. Hydrolytic cleavage of the 1,4‐diazepine fragment in [F8sPc1] is observed upon chromatography or in the presence of a strong acid (CF3COOH) and leads to 2‐amino‐3‐benzamide substituted dibenzo subporphyrazine [F8sPc2]. Fluorescence of [F8sPc1] (ΦF=0.03) is ca 10 times lower than for [F12sPc] (ΦF=0.28) due to the combined effect of intramolecular charge transfer (ICT) from the donor diazepine ring to the acceptor sPc macrocycle and heavy atom effect of chlorine. Fluorescence of [F8sPc2] is almost completely quenched by ICT from −NH2 group to the electron‐deficient subporphyrazine core (ΦF<0.001), but addition of acid leads to protonation of the amino group and switch‐ON the fluorescence. Therefore, aminobenzamide substituted subporphyrazines can be considered as perspective pH‐sensitive fluorophores.

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Section: Resultsmentioning

confidence: 99%

Section: Synthesis and Characterizationmentioning

confidence: 99%

Section: Synthesis and Characterizationmentioning

confidence: 99%

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First Subphthalocyanine Analogue with Fused 6H‐1,4‐diazepine Ring and its Conversion to Aminobenzamide Derivative

Skvortsov,

Chufarin,

Zaitsev

et al. 2023

Asian J Org Chem

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Low‐symmetry A₃B‐type 6H‐1,4‐diazepinoporphyrazines with anti‐Kasha effect as promising photosensitizers

Tarakanov,

Neganova,

Mishchenko

et al. 2024

Photochem & Photobiology

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A series of tribenzo[g,l,q]‐6H‐1,4‐diazepino[2,3‐b]porphyrazines has been synthesized. A temperature‐dependent steric effect was applied in the mixed Linstead macrocyclization of phthalonitrile and 5,7‐bis(2′‐arylethenyl)‐6‐propyl‐6H‐1,4‐diazepine‐2,3‐dicarbonitrile to achieve high yield of low‐symmetry A3B‐type Mg(II) tribenzo[g,l,q]‐6H‐1,4‐diazepino[2,3‐b]porphyrazinate. The analysis of photophysical and photochemical properties of the obtained complexes showed the anti‐Kasha effect: the ultrafast spin changes successfully compete with the IC. TD‐DFT calculations showed that the presence of 1,4‐diazepine heterocycle in the porphyrazine structure leads to the formation of additional charge‐transfer triplet state T2. We propose, it could participate in the pumping of T1x state alongside with T1y state (these states are degenerate in D4h symmetry) and, therefore, increase singlet oxygen (1Δg) generation. Stable micellar nanoparticles have been obtained based on the tribenzo[g,l,q]‐6H‐1,4‐diazepino[2,3‐b]porphyrazine Mg(II) and Zn(II) complexes using polyvinylpyrrolidone. The nanoparticles effectively interact with model biological structures (FBS and brain homogenate), leading to disaggregation of the macrocycles. They also exhibit pronounced phototoxic effects in MCF‐7 cells upon red light irradiation. We propose that enhancement in PDT activity could be explained by their increased resistance to aggregation due to the presence of n‐propyl substituent directly attached to the C6 position of the 1,4‐diazepine moiety. The demonstrated results show the promising potential of tribenzo‐6H‐1,4‐diazepinoporphyrazines as heavy atom‐free photosensitizers.

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The chemistry of heterocycles in the 21st century

Charushin,

Verbitskiy,

Chupakhin

et al. 2024

RUSS CHEM REV

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The chemistry of heterocyclic compounds has traditionally been and remains a bright area of chemical science in Russia. This is due to the fact that many heterocycles find the widest application. These compounds are the key structural fragments of most drugs, plant protection agents. Many natural compounds are also derivatives of heterocycles. At present, more than half of the hundreds of millions of known chemical compounds are heterocycles. This collective review is devoted to the achievements of Russian chemists in this field over the last 15–20 years. The review presents the achievements of leading heterocyclists representing both RAS institutes and university science. It is worth noting the wide scope of the review, both in terms of the geography of author teams, covering the whole of our large country, and in terms of the diversity of research areas. Practically all major types of heterocycles are represented in the review. The special attention is focused on the practical applications of heterocycles in the design of new drugs and biologically active compounds, high-energy molecules, materials for organic electronics and photovoltaics, new ligands for coordination chemistry, and many other rapidly developing areas. These practical advances would not be possible without the development of new fundamental transformations in heterocyclic chemistry.<br> Bibliography — 2237 references.

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Electronic and steric effects controlling monomer–dimer self-assembly in 6H-1,4-diazepinoporphyrazines: an experimental and theoretical study

Abstract: A series of 5,7-disubstituted 1,4-diazepinoporphyrazinato magnesium(II) and nickel(II) complexes, including two novel compounds, was obtained by metal‐templated macrocyclization. A combination of X-ray diffraction, 1H NMR, UV-vis, and electrochemical analyses allowed...

Cited by 3 publications

References 56 publications

First Subphthalocyanine Analogue with Fused 6H‐1,4‐diazepine Ring and its Conversion to Aminobenzamide Derivative

First Subphthalocyanine Analogue with Fused 6H‐1,4‐diazepine Ring and its Conversion to Aminobenzamide Derivative

Low‐symmetry A₃B‐type 6H‐1,4‐diazepinoporphyrazines with anti‐Kasha effect as promising photosensitizers

The chemistry of heterocycles in the 21st century

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Electronic and steric effects controlling monomer–dimer self-assembly in 6H-1,4-diazepinoporphyrazines: an experimental and theoretical study

Abstract: A series of 5,7-disubstituted 1,4-diazepinoporphyrazinato magnesium(II) and nickel(II) complexes, including two novel compounds, was obtained by metal‐templated macrocyclization. A combination of X-ray diffraction, 1H NMR, UV-vis, and electrochemical analyses allowed...

Cited by 3 publications

References 56 publications

First Subphthalocyanine Analogue with Fused 6H‐1,4‐diazepine Ring and its Conversion to Aminobenzamide Derivative

First Subphthalocyanine Analogue with Fused 6H‐1,4‐diazepine Ring and its Conversion to Aminobenzamide Derivative

Low‐symmetry A3B‐type 6H‐1,4‐diazepinoporphyrazines with anti‐Kasha effect as promising photosensitizers

The chemistry of heterocycles in the 21st century

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Low‐symmetry A₃B‐type 6H‐1,4‐diazepinoporphyrazines with anti‐Kasha effect as promising photosensitizers