Biradical with a polyfluorinated terphenylene backbone

Fedyushin, Pavel; Serykh, Andrey; Vinogradov, A. S.; Mezhenkova, T. V.; Platonov, V. Е.; Nasyrova, Darina I.; Samigullina, Aida I.; Fedin, Matvey V.; Zayakin, I. A.; Tretyakov, E. V.

doi:10.1007/s11172-022-3577-0

Cited by 8 publications

(3 citation statements)

References 55 publications

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“…The yields were based on bromopentafluorobenzene. The identity and purity of the target compounds 2-4 were confirmed by 19 F NMR spectra (Bruker AV-300 (282.40 MHz) in CHCl 3 -CDCl 3 ), which were consistent with the literature data [147][148][149]. Compound 1 was also available from alternative sources (Decafluorobiphenyl 99%, Avocado Research Chemicals Ltd., London UK), and this was used in the study.…”

Section: Methodssupporting

confidence: 65%

Recombination of X-ray-Generated Radical Ion Pairs in Alkane Solution Assembles Optically Inaccessible Exciplexes from a Series of Perfluorinated para-Oligophenylenes with N,N-Dimethylaniline

Nikul’shin

Федунов

Куйбида

et al. 2023

IJMS

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We demonstrate that a series of perfluorinated para-oligophenylenes C6F5-(C6F4)n-C6F5 (n = 1–3) produce exciplexes with N,N-dimethylaniline (DMA) in degassed X-irradiated n-dodecane solutions. The optical characterization of the compounds shows that their short fluorescence lifetimes (ca. 1.2 ns) and UV-Vis absorption spectra, overlapping with the spectrum of DMA with molar absorption coefficients of 2.7–4.6 × 104 M−1cm−1, preclude the standard photochemical exciplex formation pathway via selective optical generation of the local excited state of the donor and its bulk quenching by the acceptor. However, under X-rays, the efficient assembly of such exciplexes proceeds via the recombination of radical ion pairs, which delivers the two partners close to each other and ensures a sufficient energy deposition. The exciplex emission is completely quenched by the equilibration of the solution with air, providing a lower bound of exciplex emission lifetime of ca. 200 ns. The recombination nature of the exciplexes is confirmed by the magnetic field sensitivity of the exciplex emission band inherited from the magnetic field sensitivity from the recombination of spin-correlated radical ion pairs. Exciplex formation in such systems is further supported by DFT calculations. These first exciplexes from fully fluorinated compounds show the largest known red shift of the exciplex emission from the local emission band, suggesting the potential of perfluoro compounds for optimizing optical emitters.

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Section: Methodssupporting

confidence: 65%

Recombination of X-ray-Generated Radical Ion Pairs in Alkane Solution Assembles Optically Inaccessible Exciplexes from a Series of Perfluorinated para-Oligophenylenes with N,N-Dimethylaniline

Nikul’shin

Федунов

Куйбида

et al. 2023

IJMS

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“…In a series of other works, a trifluoromethyl group was introduced to the C7 position of the Blatter radical to give radicals with significantly improved chemical stability [38,39]. Herein, as part of our increasing interest in "structure-property" correlations inherent in fluorinated organic radicals [40][41][42][43][44][45][46][47][48][49][50][51][52], we report synthesis, structure and complete characterization of novel difluorophenyl-substituted Blatter radicals, namely 1-(3,4-difluorophenyl)-3-phenyl-1,4-dihydrobenzo[e] [1,2,4]triazin-4-yl (1a) and 1-(2,4-difluorophenyl)-3-phenyl-1,4-dihydrobenzo[e] [1,2,4]triazin-4-yl (1b).…”

Section: Introductionmentioning

confidence: 99%

Effects of Difluorophenyl Substituents on Structural, Redox, and Magnetic Properties of Blatter Radicals

et al. 2023

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Blatter radicals 1-(3,4-difluorophenyl)-(1a) and 1-(2,4-difluorophenyl)-3-phenyl-1,4-dihydrobenzo[e][1,2,4]triazin-4-yl (1b) were prepared in good yields through oxidation of the corresponding amidrazones using MnO2 in dry CH2Cl2. Cyclic voltammetry showed that both radicals are oxidized and reduced chemically and electrochemically reversibly in accordance with −1/0 and 0/+1 processes. EPR spectroscopy indicated that spin density is mainly delocalized on the triazinyl moiety of the heterocycle. The structure of all paramagnets was unambiguously confirmed by single-crystal X-ray diffraction, and two different 1D chains of alternating radicals were identified. 3,4-difluorophenyl-derivatives 1a are packed into columns composed of two kinds of alternating centrosymmetric dimers, having comparatively short intermolecular distances. In crystals of 2,4-difluorophenyl-derivative 1b, the parallel arrangement of bicyclic moieties and phenyl rings favors the formation of 1D regular chains wherein the radicals are related by translation parallel to the crystallographic stacking axis. Magnetic susceptibility measurements in the 2–300 K region showed that in crystals of the radicals, strong antiferromagnetic interactions are dominant. Subsequent fitting of the dependence of χT on T with 12-membered looped stacks gave the following best-fit parameters: for 1a, g = 2.01 ± 0.05, J1/kB = −292 ± 10 K (according to BS-DFT calculations J2 = 0.12 × J1 and J3 = 0.61 × J1); for 1b, g = 2.04 ± 0.01 J1/kB = −222 ± 17 K. For comparison, in a nonfluorinated related radical, there are only very weak intermolecular interactions along the columns (J/kB = −2.2 ± 0.2 K). These results illustrate the magnitude of the influence of the difluorophenyl substituents introduced into Blatter radicals on their structure and magnetic properties.

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“…So far, various nitronyl nitroxides have been created to construct heterospin molecule-based magnetic systems, but a comprehensive series of paramagnetic metal ions' complexes with fluorinated radicals has not been investigated. Naturally, it is to be expected that the introduction of fluorine into metal-radical systems can have a major effect on their packing in crystals, thus altering intermolecular exchange interaction channels and ultimately the parameters of magnetic materials [26][27][28][29][30][31].…”

Section: Introductionmentioning

confidence: 99%

5-Fluoro-1-Methyl-Pyrazol-4-yl-Substituted Nitronyl Nitroxide Radical and Its 3d Metal Complexes: Synthesis, Structure, and Magnetic Properties

Kudryavtseva,

Serykh,

Ugrak

et al. 2023

Crystals

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The metal–radical approach is a well-established synthetic way toward multi-spin systems that relies on the coordination of stable radical ligands with transition metal ions. The advantage offered by the use of paramagnetic ligands is that metal–radical magnetic exchange coupling is direct between the magnetic orbitals of the radical and metal ion. With the aim of further exploring this approach, crystals of four heterspin complexes, [M(hfac)2LF]2 {M = Mn, Co, or Ni and hfac = hexafluoroacetylacetonate} and [Cu(hfac)2LF]n, were obtained using a new fluorinated pyrazolyl-substituted nitronyl nitroxide radical, 4,4,5,5-tetramethyl-2-(5-fluoro-1-methyl-1H-pyrazol-4-yl)-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl (LF) as a ligand. The newly synthesized complexes were fully characterized, including X-ray crystallography and magnetometry. XRD analysis revealed that complexes [M(hfac)2LF]2 have similar dimer structures in which a metal ion is in a six-coordinated environment with four O atoms from the two hfac ligands, one radical O atom, and one pyrazole N atom from ligand LF. Nonetheless, the packing patterns of the complexes were found to be considerably different. In [Mn(hfac)2LF]2, there are no magnetically important short contacts between manganese dimers. By contrast, in [Co(hfac)2LF]2 and [Ni(hfac)2LF]2, there are short contacts between non-coordinate O atoms of nitronyl nitroxide moieties. Magnetic behaviors of [M(hfac)2LF]2 showed that the M ions and the directly coordinated radicals are strongly antiferromagnetically coupled (JMn-ON = −84.1 ± 1.5 cm−1, JCo-ON = −134.3 ± 2.6 cm−1, and JNi-ON = −276.2 ± 2.1 cm−1; H^=−2JS⃑^MS⃑^NO). Notably, the magnetization of [Mn(hfac)2LF]2 having molecular structure proved to be accompanied by hysteresis. The [Cu(hfac)2LF]n complex has a chain-polymer structure with alternating magnetic fragments: three spin exchange clusters {ONO–Cu(II)–ONO} and {Cu(II)} ions. Despite the direct coordination of radicals, its magnetic properties are weakly ferromagnetic (JCu-ON = 14.8 ± 0.3 cm−1).

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Biradical with a polyfluorinated terphenylene backbone

Cited by 8 publications

References 55 publications

Recombination of X-ray-Generated Radical Ion Pairs in Alkane Solution Assembles Optically Inaccessible Exciplexes from a Series of Perfluorinated para-Oligophenylenes with N,N-Dimethylaniline

Recombination of X-ray-Generated Radical Ion Pairs in Alkane Solution Assembles Optically Inaccessible Exciplexes from a Series of Perfluorinated para-Oligophenylenes with N,N-Dimethylaniline

Effects of Difluorophenyl Substituents on Structural, Redox, and Magnetic Properties of Blatter Radicals

5-Fluoro-1-Methyl-Pyrazol-4-yl-Substituted Nitronyl Nitroxide Radical and Its 3d Metal Complexes: Synthesis, Structure, and Magnetic Properties

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