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Reactions of open-shell molecular graphene fragments are typically thought of as undesired decomposition processes because they lead to the loss of desired features like π-magnetism. Oxidative dimerization of phenalenyl to peropyrene shows, however, that these transformations hold promise as a synthetic tool for making complex structures via formation of multiple bonds and rings in a single step. Here, we explore the feasibility of using this "undesired" reaction of phenalenyl to build up strain and provide access to non-planar polycyclic aromatic hydrocarbons. To this end, we designed and synthesized a biradical system with two phenalenyl units linked via a biphenylene backbone. The design facilitates an intramolecular cascade reaction to a helically twisted saddle-shaped product, where the key transformations-ring-closure and ring-fusion-occur within one reaction. The negative curvature of the final peropyrene product, induced by the formed eight-membered ring, was confirmed by single-crystal X-ray diffraction analysis and the helical twist was validated via resolution of the product's enantiomers that display circularly polarized luminescence and high configurational stability.
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Methyl and methylene compounds of arsenic and antimony have been studied by photoelectron photoion coincidence spectroscopy to investigate their relative stability. While for As both HAs=CH2 , As-CH3 and the methylene compound As=CH2 are identified in the spectrum, the only Sb compound observed is Sb-CH3 . Thus, there is a step in the main groupâ 15 between As and Sb, regarding the relative stability of the methyl compounds. Ionisation energies, vibrational frequencies and spin-orbit splittings were determined for the methyl compound from photoion mass-selected photoelectron spectra. Although the spectroscopic results for organoantimony resemble those for the previously investigated bismuth compounds, EPR spectroscopic experiments indicate a far lower tendency for methyl transfer for Sb(CH3 )3 compared to Bi(CH3 )3 . This study concludes investigations on low-valent organopnictogen compounds.
Asunto(s)
Antimonio , Arsénico , Espectroscopía de Fotoelectrones , Espectrometría de Masas , Antimonio/químicaRESUMEN
Differently substituted phenyl isonitriles (with C-H bonds in ortho-position) and naphthyl isonitriles were reacted with the cyclic biradical [â P(µ-N-Ter)2 Pâ ] (1). Insertion of the isonitrile formed a cyclic five-membered biradical [â P(NTer)2 C(R)Pâ ] (2R, R=phenyl, naphthyl) in the first step, followed by C-H activation at the aryl substituent, resulting in novel azaphospholes (5R), which could be isolated and fully characterized. The formation of the azaphospholes can be prevented by the addition of a second equivalent of isonitrile, which causes the blocking of the radical centers in 2R by adduct formation (3R). Quantum mechanical calculations showed that a significant increase in the aromaticity of the benzo- and naphtho-azaphospholes is one of the driving forces for the activation process leading to the formation of thermodynamically favored azaphospholes. Targeted activation of C-H bonds using biradical systems represents a new synthetic approach to generate benzo- and naphtho-azaphospholes.
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Nitroxide biradicals are efficient polarizing agents in dynamic nuclear polarization (DNP) solid-state nuclear magnetic resonance. Many recently reported radicals possess substantial DNP efficiency in organic solvents but have poor solubility in water media which is unfavorable for biological applications. In this paper, we report DNP efficiency at a high magnetic field for two water-soluble biradicals resistant to reducing media. Water solubility was achieved by obtaining the radicals in the form of quaternary ammonium salts. Parameters of hyperfine interaction and exchange interaction were quantified by EPR spectroscopy, and their influence on the DNP effect was determined. The resistance of the biradicals to strongly reducing media was characterized. High stability was achieved using tetraethyl substituents and pyrrolidine moieties.
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Campos Magnéticos , Óxidos de Nitrógeno , Espectroscopía de Resonancia Magnética/métodos , AguaRESUMEN
The activation of C-Br bonds in various bromoalkanes by the biradical [â P(µ-NTer)2 Pâ ] (1) (Ter=2,6-bis-(2,4,6-trimethylphenyl)-phenyl) is reported, yielding trans-addition products of the type [Br-P(µ-NTer)2 P-R] (2), so-called 1,3-substituted cyclo-1,3-diphospha-2,4-diazanes. This addition reaction, which represents a new easy approach to asymmetrically substituted cyclo-1,3-diphospha-2,4-diazanes, was investigated mechanistically by different spectroscopic methods (NMR, EPR, IR, Raman); the results suggested a stepwise radical reaction mechanism, as evidenced by the in-situ detection of the phosphorus-centered monoradical [â P(µ-NTer)2 P-R].< To provide further evidence for the radical mechanism, [â P(µ-NTer)2 P-Et] (3Etâ ) was synthesized directly by reduction of the bromoethane addition product [Br-P(µ-NTer)2 P-Et] (2 a) with magnesium, resulting in the formation of the persistent phosphorus-centered monoradical [â P(µ-NTer)2 P-Et], which could be isolated and fully characterized, including single-crystal X-ray diffraction. Comparison of the EPR spectrum of the radical intermediate in the addition reaction with that of the synthesized new [â P(µ-NTer)2 P-Et] radical clearly proves the existence of radicals over the course of the reaction of biradical [â P(µ-NTer)2 Pâ ] (1) with bromoethane. Extensive DFT and coupled cluster calculations corroborate the experimental data for a radical mechanism in the reaction of biradical [â P(µ-NTer)2 Pâ ] with EtBr. In the field of hetero-cyclobutane-1,3-diyls, the demonstration of a stepwise radical reaction represents a new aspect and closes the gap between P-centered biradicals and P-centered monoradicals in terms of radical reactivity.
RESUMEN
Dynamic nuclear polarization (DNP) is a powerful method to enhance the sensitivity of solid-state magnetic nuclear resonance (ssNMR) spectroscopy. However, its biomolecular applications at high magnetic fields (preferably>14â T) have so far been limited by the intrinsically low efficiency of polarizing agents and sample preparation aspects. Herein, we report a new class of trityl-nitroxide biradicals, dubbed SNAPols that combine high DNP efficiency with greatly enhanced hydrophilicity. SNAPol-1, the best compound in the series, shows DNP enhancement factors at 18.8 T of more than 100 in small molecules and globular proteins and also exhibits strong DNP enhancements in membrane proteins and cellular preparations. By integrating optimal sensitivity and high resolution, we expect widespread applications of this new polarizing agent in high-field DNP/ssNMR spectroscopy, especially for complex biomolecules.
Asunto(s)
Campos Magnéticos , Óxidos de Nitrógeno , Espectroscopía de Resonancia Magnética , Proteínas de la MembranaRESUMEN
Conversion of 1,2-bis(dichlorophosphino)benzene with sterically demanding primary amines led to the formation of 1,3-dichloro-2-aza-1,3-diphosphaindanes of the type C6 H4 (µ-PCl)2 N-R. Reduction yielded the corresponding 2-aza-1,3-diphosphaindane-1,3-diyls (1), which can be described as phosphorus-centered singlet biradical(oid)s. Their stability depends on the size of the substituent R: While derivatives with R=Dmp (2,6-dimethylphenyl) or Ter (2,6-dimesitylphenyl) underwent oligomerization, the derivative with very bulky R=tBu Bhp (2,6-bis(benzhydryl)-4-tert-butylphenyl) was stable with respect to oligomerization in its monomeric form. Oligomerization involved activation of the fused benzene ring by a second equivalent of the monomeric biradical and can be regarded as formal [2+2] (poly)addition reaction. Calculations indicate that the biradical character in 1 is comparable with literature-known P-centered biradicals. Ring-current calculations show aromaticity within the entire ring system of 1.
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Nanographenes (NGs) with tunable electronic and magnetic properties have attracted enormous attention in the realm of carbon-based nanoelectronics. In particular, NGs with biradical character at the ground state are promising building units for molecular spintronics. However, most of the biradicaloids are susceptible to oxidation under ambient conditions and photolytic degradation, which hamper their further applications. Herein, we demonstrated the feasibility of tuning the magnetic properties of zigzag-edged NGs in order to enhance their stability via the controlled Diels-Alder reactions of peri-tetracene (4-PA). The unstable 4-PA (y0 =0.72; half-life, t1/2 =3â h) was transformed into the unprecedented benzo-peri-tetracenes (BPTs) by a one-side Diels-Alder reaction, which featured a biradical character at the ground state (y0 =0.60) and exhibited remarkable stability under ambient conditions for several months. In addition, the fully zigzag-edged circumanthracenes (CAs) were achieved by two-fold or stepwise Diels-Alder reactions of 4-PA, in which the magnetic properties could be controlled by employing the corresponding dienophiles. Our work reported herein opens avenues for the synthesis of novel zigzag-edged NGs with tailor-made magnetic properties.
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We report infrared spectra of xylylene isomers in the gas phase, using free electron laser (FEL) radiation. All xylylenes were generated by flash pyrolysis. The IR spectra were obtained by monitoring the ion dip signal, using a IR/UV double resonance scheme. A gas phase IR spectrum of para-xylylene was recorded, whereas ortho- and meta-xylylene were found to partially rearrange to benzocyclobutene and styrene. Computations of the UV oscillator strength for all molecules were carried out and provde an explanation for the observation of the isomerization products.
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Narrow HOMO-LUMO gaps and high charge-carrier mobilities make larger acenes potentially high-efficient materials for organic electronic applications. The performance of such molecules was shown to significantly increase with increasing number of fused benzene rings. Bulk quantities, however, can only be obtained reliably for acenes up to heptacene. Theoretically, (oligo)acenes and (poly)acenes are predicted to have open-shell singlet biradical and polyradical ground states, respectively, for which experimental evidence is still scarce. We have now been able to dramatically lower the HOMO-LUMO gap of acenes without the necessity of unfavorable elongation of their conjugated πâ system, by incorporating two boron atoms into the anthracene skeleton. Stabilizing the boron centers with cyclic (alkyl)(amino)carbenes gives neutral 9,10-diboraanthracenes, which are shown to feature disjointed, open-shell singlet biradical ground states.
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Diindeno-fused dibenzo[a,h]anthracene 6 and diindeno-fused dibenzo[c,l]chrysene 9 contain the key moieties 1,4-quinodipropene (1,4-QDP) and 2,6-naphthoquinodipropene (2,6-NQDP), respectively, and they both have an open-shell singlet ground state. The latter compound exhibits a strong biradical character and interesting properties, including a low ΔET-S (2.44â kcal mol-1 ), a small HOMO-LUMO gap (1.06â eV), a wide photoabsorption range (250-1172â nm), and a large two-photon absorption cross-section (σ=1342±56 GM). This work verifies that 6 has a slightly larger HOMO-LUMO gap and ΔET-S than its helical isomer diindeno[2,1-f:1',2'-j]picene (DIP), but is a much stronger two-photon absorber, verifying the important effect of geometry on the photophysical properties.
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The reactivity of the four-membered NP3 ring system [RN(µ-PCl)2 PR] (R=Mes*=2,4,6-tri-tert-butylphenyl) towards Lewis acids, Lewis bases, and reducing agents was investigated. Comparisons with the literature-known, analogous cyclic compounds [ClP(µ-NR)]2 (R=Ter=2,6-dimesitylphenyl) and [ClP(µ-PR)]2 (R=Mes*) are drawn, to obtain a better systematic understanding of the reactivity of cyclic NP species. Apart from experimental results, DFT computations are discussed to further the insight into bonding and electronic structure of these compounds.
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The first isoindigo (bi)radicals were obtained by proton coupled oxidation of their 4-hydroxyaryl substituted precursors. Optical and magnetic spectroscopic studies revealed a singlet open-shell biradicaloid electronic ground state for the bisphenoxyl-isoindigo (
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Three new and stable diradical dications based on the 4,10-dibromoanthanthrone have been synthesized and characterized. In their dicationic state, the amines show a biradical character in the ground state. Their magnetic properties have been investigated by NMR and EPR spectroscopies. The dicationic salts shows strong and broad optical absorption in the near-infrared region. The main driving force to obtain a ground state biradical is the high steric hindrance that prevents planarization of the diphenylamines with the anthanthrone aromatic core. The radical cations are isolated in two perpendicular π-systems as demonstrated by X-ray diffraction structures. This work provides a new bridging unit in the search for biradical bis(triarylamines) salts.
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Installing π-functional substituents on the skeletal phosphorus atoms of the air-tolerant 1,3-diphosphacyclobutane-2,4-diyl unit are promising for tuning the open-shell singlet P-heterocyclic chromophore. The sterically encumbered 1,3-diphosphaCycloButen-4-yl Anion (CBA), generated from the phosphorus-carbon triple bond, was available for the regioselective arylation via nucleophilic aromatic substitution (SN Ar) reaction, addition to arynes, and single-electron transfer (SET) process affording the corresponding P-arylated 1,3-diphosphacyclobutane-2,4-diyls. The photo-absorption and redox properties correlated with the effects of the aryl substituents on the 1,3-diphosphacyclobutane-2,4-diyl unit. The X-ray analyses enabled not only to discuss the metric parameters but also to visualize the radicalic electrons via the electron-density distribution analysis. The electron-donating character of the P-heterocyclic chromophores induced the p-type semiconductor behavior. Detection of hydrogen fluoride via formation of the 1λ5 ,3λ5 -diphosphete derivative was also developed.
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The thermal gas-phase reactions of [ReO4 ]+ with methane have been explored by using Fourier Transform Ion Cyclotron Resonance (FT-ICR) mass spectrometry complemented by high-level quantum chemical calculations. Upon reacting with methane, this cluster oxide, having an even-number of valence electrons, brings about both hydrogen-atom abstraction (HAT) to generate [ReO4 H].+ and the formation of formaldehyde. Mechanistically, HAT occurs on the ground-state triplet surface, while for the generation of formaldehyde a two-state reactivity scenario prevails. The branching ratio of these competing processes is affected by the rather inefficient spin-orbit coupling to bring about the required triplet-singlet intersystem crossing.
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We report the first example of tuning the large magneto-optic activity of a chiral polymer by addition of stable organic biradicals. The spectral dispersion of Verdet constant, which quantifies magneto-optic response, differs substantially between the base polymer and the nanocomposite. We employed a microscopic model, supported by atomistic calculations, to rationalize the behavior of this nanocomposite system. The suggested mechanism involves magnetic coupling between helical conjugated polymer fibrils, with spatially delocalized helical π-electron density, and the high density of spin states provided by the biradical dopants, which leads to synergistic enhancement of magneto-optic response. Our combined experimental and theoretical studies reveal that the manipulation of magnetic coupling in this new class of magneto-optic materials offers an opportunity to tailor the magnitude, sign, and spectral dispersion of the Verdet constant over a broad range of wavelengths, from the UV to the near-IR. This provides a new strategy for creating conformable materials with extraordinary magneto-optic activity, which can ultimately enable new applications requiring spatially and temporally resolved measurement of extremely weak magnetic fields. In particular, magneto-optic materials, presently employed in technologies like optical isolators and optical circulators, could be used in ultrasensitive optical magnetometers. This, in turn, could open a path toward mapping of brain activity via optical magnetoencephalography.
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Diindeno-fused bischrysene, a new diindeno-based polycyclic hydrocarbon (PH), was synthesized and characterized. It was elucidated in detailed experimental and theoretical studies that this cyclopenta-fused PH possesses an open-shell singlet biradical structure in the ground state and exhibits high stability under ambient conditions (t1/2 =39â days). The crystal structure unambiguously shows a novel saddle-shaped π-conjugated carbon skeleton due to the steric hindrance of the central cove-edged bischrysene unit. UV/Vis spectral measurements revealed that the title molecule has a very narrow optical energy gap of 0.92â eV, which is consistent with the electrochemical analysis and further supported by density functional theory (DFT) calculations.
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Among the numerous routes organic chemists have developed to synthesize benzene derivatives and heteroaromatic compounds, transition-metal-catalyzed cycloaddition reactions are the most elegant. In contrast, cycloaddition reactions of heavier alkene and alkyne analogues, though limited in scope, proceed uncatalyzed. In this work we present the first spontaneous cycloaddition reactions of lighter alkene and alkyne analogues. Selective addition of unactivated alkynes to boron-boron multiple bonds under ambient conditions yielded diborocarbon equivalents of simple aromatic hydrocarbons, including the first neutral 6 π-aromatic diborabenzene compound, a 2 π-aromatic triplet biradical 1,3-diborete, and a phosphine-stabilized 2 π-homoaromatic 1,3-dihydro-1,3-diborete. DFT calculations suggest that all three compounds are aromatic and show frontier molecular orbitals matching those of the related aromatic hydrocarbons, C6 H6 and C4 H4 (2+) , and homoaromatic C4 H5 (+) .
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The electronic structure of the simplest Criegee intermediate, H2COO, is practically that of a closed shell. On the biradical scale (ß), where 0 corresponds to the pure closed shell and 1 to a pure biradical, its ßâ value is only 0.10, suggesting that its ground electronic state is best described as a H2C=O(δ+)-O(δ-) zwitterion. However, this picture of a nearly inert closed shell contradicts its rich reactivity in the atmosphere. It is shown that the mixing of its ground state with the first triplet excited state, which is a pure biradical state of the type H2CË-O-OË, is responsible for the formation of strongly bound products during reactions inducing atmospheric particle growth.