RESUMO
Organic radicals exhibit great potential in photothermal applications, however, their innate high reactivity with oxygen renders the preparation of stable organic radicals highly challenging. In this work, a series of co-doped radical polymers ares prepared by doping dihydrophenazine derivatives (DPPs) into the epoxy resin matrix. DPPs can form radical species through the electron transfer process, which are further stabilized by the complex 3D network structure of epoxy resin. Experimental results show that the photothermal conversion efficiency is as high as 79.9%, and the temperature can quickly rise to ≈130 °C within 60 s. Due to the excellent visible light transmittance and mechanical properties of co-doped systems, this study further demonstrates their practical applications in energy-saving solar windows and thermoelectric power generation.
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Herein a series of chiral BTI radical anions bearing different chiral substituents were efficiently prepared by chemical reduction. X-ray crystallography revealed finely-tuned packing and helix assemblies of the radicals by the size of chiral substituents in crystalline state. In accordance with the crystalline-state packing, the powder ESR spectra indicate that 4 a- â CoCp2 + and 4 c- â CoCp2 + π-dimers exhibit thermally excited triplet states arising from strong spin-spin interactions, while discrete 4 b- â CoCp2 + shows a broad doublet-state signal reflecting weak spin-spin interactions. The interplay between the unpaired electron spin and chiral substituents was studied by UV-Vis-NIR spectra, electronic circular dichroism (ECD) and TD DFT calculations. Different NIR absorptions of the radicals attributing to isolated SOMOâLUMO+1 (~889â nm) transitions were recorded. The emergence of Cotton effects (CEs) at the NIR region for 4 c- â CoCp2 + radical enantiomers suggest the interplay between chirality and unpaired electron spin. The origin of the different circularly polarized light absorptions regarding SOMO derived transitions (around 880â nm) was attributed to chiral substitutes regulated electric and magnetic transition dipole moments of the unpaired electron participated transition.
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The spin theory of fullerenes is taken as a basis concept to virtually exhibit a peculiar role of C60 fullerene in the free radical polymerization of vinyl monomers. Virtual reaction solutions are filled with the initial ingredients (monomers, free radicals, and C60 fullerene) as well as with the final products of a set of elementary reactions, which occurred in the course of the polymerization. The above objects, converted to the rank of digital twins, are considered simultaneously under the same conditions and at the same level of the theory. In terms of the polymerization passports of the reaction solutions, a complete virtual picture of the processes considered is presented.
Assuntos
Fulerenos , Polimerização , Radicais Livres , Cloreto de PolivinilaRESUMO
A new, 19 π-delocalized electrons planar Blatter radical building block was developed and used to obtain paramagnetic bent-core liquid crystals. The mesogens were investigated by optical, thermal, powder XRD and DFT methods in the pure form and as binary mixtures. Comparison of their properties with those of the classical Blatter radical analogues revealed that planarization of the central angular element results in a significantly higher stability of the mesophases and increased molecular organization suitable for the formation of ordered banana and columnar mesophases with tighter π-π interactions. These results indicate access to a new, potentially rich class of functional paramagnetic soft materials.
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A simple and highly effective methodology for the cross-coupling of heteroaryl iodides with NN-AuPPh3 at room temperature is reported. The protocol is based on a novel catalytic system consisting of Pd2(dba)3·CHCl3 and the phosphine ligand MeCgPPh having an adamantane-like framework. The present protocol was found to be well compatible with various heteroaryl iodides, thus opening new horizons in directed synthesis of functionalized nitronyl nitroxides and high-spin molecules.
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A series of carbazole-dendronized tris(2,4,6-trichlorophenyl)methyl (TTM) radicals have been synthesized. The photophysical properties of dendronized radicals up to the fourth generation were compared systematically to understand how structure-property relationships evolve with generation. The photoluminescence quantum yield (PLQY) was found to increase with the increasing generation, and the fourth generation (G4TTM) in cyclohexane solution showed a PLQY as high as 63 % at a wavelength of 627â nm (in the deep-red region) from the doublet state. The dendron modification strategy also showed a blue-shift of the emission on increasing the generation number, and the photostability was also increased compared to the bare TTM radical.
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Stable carbon-based polyradicals exhibiting strong spin-spin coupling and slow depolarization processes are particularly attractive functional materials. A new molecular motif synthesized by a convenient method that allows the integration of stable, high-spin radicals to (hetero)aromatic polycycles has been developed, as illustrated by a non-Kekulé diradical showing a triplet ground state with long persistency (τ1/2 ≈31â h) in air. Compared to the widely used 1,3-phenylene, the newly designed (diaza)pyrene-4,10-diyl moiety is for the first time demonstrated to confer ferromagnetic (FM) spin coupling, allowing delocalized non-disjoint SOMOs. With the X-ray crystallography unambiguously proving the diradical structure, the triplet ground state was thoroughly characterized. A large ΔES-T of 1.1â kcal/mol, proving the strong FM coupling effect, was revealed consistently by superconducting quantum interference device (SQUID) measurements and variable-temperature electron paramagnetic resonance (EPR) spectroscopy, while the zero-field splitting and triplet nutation characters were examined by continuous-wave and pulsed EPR spectroscopy. A millisecond spin-lattice relaxation time was also detected. The current study not only offers a new molecular motif enabling FM coupling between carbon-based spins, but more importantly presents a general method for installing stable polyradicals into functional π-systems.
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Both organic radicals and organoboron reagents have been broadly investigated, but the combination of them via direct C-H borylation as organic radical building blocks has never been achieved. Herein, a series of organoradical boron reagents, such as TTM-Bpin and TTM-BOH, were synthesized through the key step of C-H borylation of substrate TTM-H ((2,6-dichlorophenyl) bis(2,4,6-trichlorophenyl)methyl) radical for the first time. They are air stable enough to be stored in the solid state for several months under dark conditions, and fully investigated through single crystal analysis, EPR and DFT calculations. Furthermore, they can smoothly work in the standard Suzuki-Miyaura coupling (SMC) reaction with retention of the carbon radical center. Meanwhile, these radical species bearing different boron units display fluorescent character and are potentially applied for the collective synthesis of luminescent organic radicals, as well as other functionalized open-shell materials.
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The preparation of radicals with intense and redox-switchable absorption beyond 1000â nm is a long-standing challenge in the chemistry of functional dyes. Here we report the preparation of a series of unprecedented stable neutral nickel(II) and copper(II) complexes of "Manitoba dipyrromethenes" (MB-DIPYs) in which the organic chromophore is present in the radical-anion state. The new stable radicals have an intense absorption at λmax â¼1300â nm and can be either oxidized to regular [MII (MB-DIPY)]+ (M=Cu or Ni) or reduced to [MII (MB-DIPY)]- compounds. The radical nature of the stable [MII (MB-DIPY)] complexes was confirmed by EPR spectroscopy with additional insight into their electronic structure obtained by UV-Vis spectroscopy, electro- and spectroelectrochemistry, magnetic measurements, and X-ray crystallography. The electronic structures and spectroscopic properties of the radical-based chromophores were also probed by density functional theory (DFT) and time-dependent DFT (TDDFT) calculations. These nickel(II) and copper(II) complexes represent the first stable radical compounds with a MB-DIPY ligand.
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The photocatalytic activity of TiO2 nanoparticles in aqueous solutions is commonly evaluated by monitoring the rate of methylene blue bleaching and phenols degradation, but both substrates suffer from many drawbacks, e.g., the high capacity of dark adsorption, self-degradation, and photosensitization. Besides, filtration is always required to separate the particulate photocatalyst before the analysis. Herein, we investigated the potential use of electron paramagnetic resonance (EPR) and 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPOL) to directly monitor the photocatalytic activity of TiO2 suspensions without the need for filtration. The results showed that TEMPOL aqueous solution is in the dark and under UV-A illumination, does not absorb UV-A and visible light, and has negligible dark adsorption. The influence of TEMPOL concentration, light intensity, and TiO2 loading on the photocatalytic deactivation rate has been investigated. The mechanisms of TEMPOL deactivation in the presence and absence of oxygen as well as in the presence of methanol â¢OH radicals' scavenger have been discussed. The photocatalytic deactivation products have been analyzed using EPR, 1H-NMR, and 13C-NMR spectroscopies. It is found that the deactivation of TEMPOL is initiated by â¢OH radicals and α-H abstraction from the 4-piperidine position followed by the formation of TEMPONE (4-oxo-2,2,6,6-tetramethylpiperidine-1-oxyl) and 4-oxo-2,2,6,6-tetramethylpiperidine). In the presence of methanol, the formed α-hydroxyl radicals (â¢CH2OH) attack the nitroxide side of TEMPOL and produce 4-hydroxy-tetramethylpiperidine. Same activity trends have been observed for the photocatalytic methanol oxidation and TEMPOL deactivation over different types of TiO2 photocatalysts evincing that the proposed method has a potential for direct monitoring of the activities of photocatalyst suspensions.
Assuntos
Metanol , Espectroscopia de Ressonância de Spin EletrônicaRESUMO
Synthetic access to 7-CF3-1,4-dihydrobenzo[e][1,2,4]triazin-4-yl radicals containing 4-(6-hydroxyhexyloxy)phenyl, 4-hydroxymethylphenyl or 3,5-bis(hydroxymethyl)phenyl groups at the C(3) position and their conversion to tosylates and phosphates are described. The tosylates were used to obtain disulfides and an azide with good yields. The Blatter radical containing the azido group underwent a copper(I)-catalyzed azide-alkyne cycloaddition with phenylacetylene under mild conditions, giving the [1,2,3]triazole product in 84% yield. This indicates the suitability of the azido derivative for grafting Blatter radical onto other molecular objects via the CuAAC "click" reaction. The presented derivatives are promising for accessing surfaces and macromolecules spin-labeled with the Blatter radical.
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High-spin conjugated radicals have great potential in magnetic materials and organic spintronics. However, to obtain high-spin conjugated radicals is still quite challenging due to their poor stability. We report the successful synthesis and isolation of a stable triplet conjugated diradical, 10,12-diaryldiindeno[1,2-b:2',1'-e]pyrazine (m-DIP). With the m-xylylene analogue skeleton containing electron-deficient sp2 -nitrogen atoms, m-DIP displays significant aromatic character within its pyrazine ring and its spin density mainly delocalizes on the meta-pyrazine unit, making it a triplet ground state conjugated diradical. Our work provides an effective "spin density tuning" strategy for stable high-spin conjugated radicals.
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The α-methylcyclopropyl (MCP) group with conformationally dependent electronic properties is suggested as an additional structural "instrument" for stabilization of both open-shell and ionic states of diarylnitroxides, to be used as "ambipolar" redox active materials. New MCP-substituted diphenylnitroxides (fully characterized by electrochemical, spectral, and X-ray data) are the most stable nitroxides of the diaryl type known to date [τ1/2 in benzene exceeds three months (2310â h)]. The radicals are capable to reversible oxidation and reduction, yielding stable oxoammonium cations and aminoxyl anions. DFT investigation of the electronic structure and geometry of the compounds confirmed the conformational switching of the cyclopropyl orientation relative to the adjacent aromatic π system is dependent on the nitroxide's redox state. Additional through-space stabilizing interaction between the π-acceptor orbital of the NO+ moiety and the cyclopropyl "banana" bond orbital was also detected, highlighting its good hyperconjugative ability. The estimated σ(para)MCP value (-0.32) confirms its strong electron-donating properties.
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A homologous series of disc-like 1,3,6-trisubstituted benzo[e][1,2,4]triazin-4-yls 1[n] was synthesized and their structural, thermal, optical, magnetic, and electric properties were investigated. The results demonstrate that all members of the series display a Colh phase with clearing temperatures depending on the length of the alkoxy chains at the N(1) position, hence the shape of the disc. Powder XRD and magnetic data indicate a gradual change in the column diameter and magnetic behavior in the series in transition from half-disc in 1[0] (antiferromagnetic interactions) to full-disc geometry in the 1[12] homologue (ferromagnetic interactions with J/kB =+7.5â K). Studies of binary systems revealed that a 1 : 1 mixture of 1[0] and 1[12] exhibits modest stabilization of the Colh phase with an expanded range, and magnetic behavior typical for 1[0] in the rigid phase obtained from the melt. Electric measurements demonstrated hole mobility of â¼10-3 â cm2 â V-1 s-1 and dark conductivity of â¼10-11 â Scm-1 in the mixture and individual compounds. The latter is enhanced up to 4 times by simultaneous illumination with UV light.
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Reversible solution π-dimerization is observed in the stable neutral phenoxyl radical 2,6-bis-(8-quinolylamino)-4-(tert-butyl)phenoxyl baqp and is spectroscopically characterized. This behavior, not previously observed for π-extended phenoxyl radicals, is relevant to the formation of long multicenter bonding in the π-dimer at low temperature akin to previously reported phenalenyl radicals. Our experimental data are supported in a quantitative manner by results from density functional theory (DFT) and ab initio molecular orbital theory calculations. Our theoretical results indicate that the solution dimer features strong bonding interactions between the two phenoxyl rings but that the stability of the dimer is also related to dispersion interactions between the flanking nearly parallel quinolyl rings.
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3-Phenyl-1,4-dihydrobenzo[e][1,2,4]triazinyl radicals with the N(1) position substituted with naphth-2-yl (1 b), naphth-1-yl (1 c), pyren-1-yl (1 d), anthracen-9-yl (1 e), 2-trifluoromethylphenyl (1 f), 3-trifluoromethylphenyl (1 g), and 2-iodophenyl (1 h) were characterized by using single-crystal X-ray diffraction, variable-temperature magnetic susceptibility, and DFT computational methods. The substituent at N(1) is essentially orthogonal to the heterocycle plane in 1 f and 1 h, and with a high torsion angle in 1 c and 1 d. Radicals 1 c and 1 h form unusual infinite chains with crisscrossing hetero-co-facial π-π interactions, whereas radical 1 d forms analogous homo-co-facial arrangements. Infinite chains of homo-co-facial π-π dimers are found in 1 b, 1 f and 1 g; in the latter the position of the CF3 group controls the slippage of the dimers in the chain. No π-π parallel arrangements were found in 1 e. Magnetic susceptibility measurements demonstrated strong antiferromagnetic interactions in 1 b (J=-264±4â cm-1 ) and 1 f (J=-134±1â cm-1 ), while weak intradimer ferromagnetic interactions were found in 1 g (J2 =+21±1 and J1 =-15±1â cm-1 ). Other derivatives exhibit typical weak antiferromagnetic exchange interactions in a range of -5 to -10â cm-1 .
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BACKGROUND: UV irradiation has ionisation character and leads to the generation of reactive oxygen species (ROS). The destructive character of ROS was observed among others during interaction of cereal grains with ozone and was caused by changes in structures of biomolecules leading to the formation of stable organic radicals. That effect was more evident for stress sensitive genotypes. In this study we investigated the influence of UV irradiation on cereal grains originating from genotypes with different tolerance to oxidative stress. RESULTS: Grains and their parts (endosperm, embryo and seed coat) of barley, wheat and oat were subjected to short-term UV irradiation. It was found that UV caused the appearance of various kinds of reactive species (O2-⢠, H2 O2 ) and stable radicals (semiquinone, phenoxyl and carbon-centred). Simultaneously, lipid peroxidation occurred and the organic structure of Mn(II) and Fe(III) complexes become disturbed. CONCLUSIONS: UV irradiation causes damage of main biochemical structures of plant tissues, the effect is more significant in sensitive genotypes. In comparison with ozone treatment, UV irradiation leads to stronger destruction of biomolecules in grains and their parts. It is caused by the high energy of UV light, facilitating easier breakage of molecular bonds in biochemical compounds. © 2017 Society of Chemical Industry.
Assuntos
Avena/efeitos da radiação , Grão Comestível/efeitos da radiação , Hordeum/efeitos da radiação , Triticum/efeitos da radiação , Avena/química , Avena/metabolismo , Grão Comestível/química , Grão Comestível/genética , Grão Comestível/metabolismo , Espectroscopia de Ressonância de Spin Eletrônica , Irradiação de Alimentos , Genótipo , Hordeum/química , Hordeum/genética , Hordeum/metabolismo , Estresse Oxidativo , Espécies Reativas de Oxigênio/metabolismo , Triticum/química , Triticum/genética , Triticum/metabolismo , Raios UltravioletaRESUMO
A reactive radical species, nitric oxide (NO), was encapsulated in a unimolecular form inside an open-cage fullerene derivative under high-pressure conditions in the solid state. Surprisingly, the molecular complex showed sharp 1 Hâ NMR signals despite the existence of the paramagnetic species inside the carbon cage. Owing to the paramagnetic shifts, the escape rate of the NO was determined experimentally. After constructing a stopper on the rim of the opening, the NO was found to stay inside the cage even at 50 °C. The ESR measurements of the powdery sample showed paramagnetic properties at low temperature. The single-crystal X-ray structure analysis clearly demonstrated the existence of the encapsulated NO molecule, suggesting rapid rotation inside the cage. The 1 Hâ NMR chemical shifts displayed a large temperature dependence owing to the paramagnetic effects.
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10,15,20-Tris(pentafluorophenyl)-substituted NiII -porphyrin meso-oxy radical bearing two coordinating pyridines was synthesized as a stable radical with a quartet ground state (S=3/2). X-ray structural analysis revealed that the NiII porphyrin moiety is fairly planar and the Ni-N bond lengths are considerably longer, indicating the high-spin state of the NiII center. The radical exhibited a quartet ground state, indicating the ferromagnetic interaction between the high-spin NiII center (S=1) and the porphyrin meso-oxy radical (S=1/2).
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Most aminyl radicals studied so far are resonance-stabilized by neighboring heteroatoms, and those without such stabilization are usually short-lived. We report herein that subporphyrin meso-2,4,6-trichlorophenylaminyl radicals and a bis(5-subporphyrinyl)aminyl radical are fairly stable under ambient conditions without such stabilization. The subporphyrin meso-2,4,6-trichlorophenylaminyl radical crystal structure displays a characteristically short Cmeso -N bond and a perpendicular arrangement of the meso-arylamino group. The stabilities of these radicals have been ascribed to extensive spin delocalization over the subporphyrin π-electronic network as well as steric protection around the aminyl radical center.