Anthracene Radical Cations Research Articles

Solid-State Synthesis of Zeolite-Templated Carbons

The first solid-state synthesis of zeolite-templated carbons (ZTCs) is reported using anthracene as the carbon precursor in FAU-structured zeolite. The evolution of the anthracene molecule upon sublimation inside of the zeolite micropore system and its further condensation into larger polyaromatic species could be followed by DRUV and Raman spectroscopy. The development of the anthracene radical cation through spontaneous charge separation was found to play a fundamental role in the formation of the carbon skeleton. A cyclic radical formation and recombination behavior could be revealed by in situ EPR spectroscopy. Textural and chemical characterization of the hybrid (zeolite/ZTC) and ZTC upon zeolite removal allowed us to conclude that anthracene allows for achieving ZTC materials with transcribed morphological and textural properties of the template zeolite. The impact of the thermal treatment on the ZTC properties was further studied. ZTCs with emerging structural order could be achieved.

Effect of protonation on the UV/VUV photostability of cyano-substituted anthracene and phenanthrene

Context. The vacuum ultraviolet (VUV) photoprocessing of polycyclic aromatic hydrocarbons (PAHs) has been established as a key piece of the puzzle to understand the life cycle of carbon-based molecules in space. The recent detection of cyano (CN) aromatic species, with unexpectedly high abundance, motivated the current study of investigating their interaction with UV/VUV radiation. Aims. The aims were to investigate the fate, after VUV photoexcitatation, of medium-size (three rings) CN-PAH radical cations and of their protonated analogs, and thus to assess the effect of protonation on the photostability of the CN-PAHs. Photoproducts (ionic fragments and dications) were mass-analyzed and measured as a function of photon energy. The results were also compared with those for the bare anthracene radical cation to assess the influence of the added CN group. Methods. The positively charged CN-PAHs were stored in a quadrupole ion trap prior to interrogation by UV/VUV radiation, with photon energies between 4.5 and 13.6 eV, delivered by the DESIRS beamline from the synchrotron SOLEIL. Results. The HCN/HNC loss channel is present for both radical cations and protonated species, but H2 loss is only apparent for the radical cations. Based on comparison with quantum chemical calculations, radiative and/or collisional processes should be relevant at energies lower than 8 eV, with a stronger propensity for radical cation than protonated CN-PAHs. The cata-condensed 9-CN-anthracene has a nearly two-fold larger photoionization yield at 13.6 eV than peri-condensed 9-CN-phenanthrene. Conclusions. The photoionization yield of singly and doubly ionized CN-PAHs is greater for radical cations than for protonated analogs. The photoionization yields of CN-PAHs is diminished by protonation and, in the future, similar investigations should target larger protonated CN-PAHs to support a general model for the photo-processing of these relevant molecular systems. Similar processes to those for the bare PAH radical cations may involve the radical cations of CN-PAHs, making their addition important in models that describe the photoelectric heating of interstellar gas.

Solar light mediated anthracene abatement in aerated aqueous media using a thermoplastic nanocomposite photocatalyst.

Polycyclic aromatic hydrocarbons (PAHs) are the most widespread xenobiotic pollutants in water and their abatement usually involves expensive and energy-consuming treatments. In this work, anthracene (AN) was selected as the recalcitrant model of PAHs and its solar light-stimulated heterogeneous photocatalytic abatement in aerated aqueous media was investigated using a new TiO2 derived thermoplastic nanocomposite in thin film form. The results were also compared with the benchmark TiO2 photocatalyst in slurry form. Finally, the possible contribution of reactive intermediates such as hydroxyl radical, AN radical cation and singlet oxygen, was investigated by using a hydroxyl radical trap and laser flash photolysis. Based on the obtained results, a feasible mechanism for AN photodegradation, which involves hydroxyl radical as the key oxidizing species is proposed.

Acid Catalysis in the Oxidation of Substrates by Mononuclear Manganese(III)-Aqua Complexes.

Acids are known to enhance the reactivities of metal-oxygen intermediates, such as metal-oxo, -hydroperoxo, -peroxo, and -superoxo complexes, in biomimetic oxidation reactions. Although metal-aqua (and metal-hydroxo) complexes have been shown to be potent oxidants in oxidation reactions, acid effects on the reactivities of metal-aqua complexes have never been investigated previously. In this study, a mononuclear manganese(III)-aqua complex, [(dpaq5NO2)MnIII(OH2)]2+ (1; dpaq5NO2 = 2-[bis(pyridin-2-ylmethyl)]amino-N-quinolin-8-ylacetamidate with an NO2 substituent at the 5 position), which is relatively stable in the presence of triflic acid (HOTf), is used in the investigation of acid-catalyzed oxidation reactions by metal-aqua complexes. As a result, we report a remarkable acid catalysis in the six-electron oxidation of anthracene by 1 in the presence of HOTf; anthraquinone is formed as the product. In the HOTf-catalyzed six-electron oxidation of anthracene by 1, the rate constant increases linearly with an increase of the HOTf concentration. Combined with the observed one-electron oxidation product, anthracene (derivative) radical cation, and the substitution effect at the 5 position of the dpaq ligand in 1 on the rate constants of the oxidation of anthracene, it is concluded that the oxidation of anthracene occurs via an acid-promoted electron transfer (APET) from anthracene to 1. The dependence of the rate constants of the APET from electron donors, including anthracene derivatives, to 1 on the driving force of electron transfer is also shown to be well fitted by the Marcus equation of outer-sphere electron transfer. To the best of our knowledge, this is the first example showing acid catalysis in the oxidation of substrates by metal(III)-aqua complexes.

Highly Conducting and Flexible Radical Crystals.

Together with high conductivity, high flexibility is an important property required for next generation organic electronic components. Both properties are difficult to achieve together especially when the components are crystalline because of the intrinsic high brittleness of organic molecular crystals. We report an organic radical crystal system that has both high flexibility and high conductivity. The crystal consists of 9,10-bis(phenylethynyl)anthracene radical cation (BPEA.+ ) units, and shows flexibility under pressure with high conductivity in ambient condition exhibiting average conductivity of 2.68 S cm-1 when normal linear shape, as well as 2.43 S cm-1 when bent. The structural analysis reveals that both a short π-π distance (3.290 Å) between BPEA.+ units that are aligned along the crystal length direction, and the presence of PF6 - counter ions induce flexibility and high electrical conductivity.

Highly Conducting and Flexible Radical Crystals

AbstractTogether with high conductivity, high flexibility is an important property required for next generation organic electronic components. Both properties are difficult to achieve together especially when the components are crystalline because of the intrinsic high brittleness of organic molecular crystals. We report an organic radical crystal system that has both high flexibility and high conductivity. The crystal consists of 9,10‐bis(phenylethynyl)anthracene radical cation (BPEA.+) units, and shows flexibility under pressure with high conductivity in ambient condition exhibiting average conductivity of 2.68 S cm−1 when normal linear shape, as well as 2.43 S cm−1 when bent. The structural analysis reveals that both a short π–π distance (3.290 Å) between BPEA.+ units that are aligned along the crystal length direction, and the presence of PF6− counter ions induce flexibility and high electrical conductivity.

The Consequences of Twisting Nanocarbons: Lessons from Tethered Twisted Acenes.

The properties of polycyclic aromatic hydrocarbons are determined by their size, shape, and functional groups. Equally important is their curvature, since deviation from planarity can affect their optical, electronic, and magnetic properties and also induce chirality. Acenes, which can be viewed as one-dimensional nanocarbons, are often twisted out of planarity. Although twisting is expected to affect the above-mentioned properties, it is often overlooked. This Account focuses on helically locked twistacenes (twisted acenes) having different twist angles and the effect of twisting on their electronic and optical properties. Various synthetic approaches to inducing backbone twist in acenes are discussed, with a focus on the introduction of a diagonal tether across the core, as this minimizes confounding substituent effects. Using such tethered acenes as our model, we then discuss the effects of twisting the aromatic core on twistacene properties. Electronic properties. Increasing the degree of twist only slightly affects the HOMO and LUMO energy levels. Twisting leads to a small increase in the HOMO level and a decrease in the LUMO level, which produces an overall decrease in the HOMO-LUMO gap. Optical properties. As the degree of twist increases, a slight bathochromic shift is observed in the absorption spectra, in accordance with the decrease in the HOMO-LUMO gap. The fluorescence quantum efficiencyandthe fluorescencelifetime also decrease. This is likely to be related to an increasing rate of intersystem crossing, which arises from increased spin-orbit coupling. In addition, computational studies indicate that the S0-T1 energy gap decreases with increasing twist. Chiroptical properties. Increased twisting results in a larger Cotton effect and anisotropy factor, with the anisotropy factors of Ant-Cn being higher than those of longer helicenes. The parallel orientation of electric and magnetic transition dipole moments in twistacenes underlies this behavior and renders them as excellent chiroptical materials. The same trend is observed for the radical cations of twistacenes, which absorb in the NIR spectral region. Conjugation and delocalization. Twisting the anthracene radical cation up to 40° (13° per benzene ring) does not significantly affect spin delocalization, with the EPR spectra of twistacene radical cations showing that only slight localization occurs. This is in line with computational studies, which show only a small decrease in π-overlap for large acene twist. Overall, modifying the length of the tether in diagonally tethered acenes allows chemists to control core twist and to induce chirality. Twisting affects key optical, electronic, and chiroptical properties of acenes. Consequently, controlling the twist angle can improve the future design of nanocarbons with desired properties.

Energy and electron transfer reactions on silica gel and titania\u2013silica mixed oxide surfaces

The energy and electron transfer reactions of anthracene co-adsorbed with an electron donor on silica gel and titania–silica mixed oxides have been studied by a combination of steady-state reflectance, emission spectroscopy, and nanosecond diffuse reflectance laser flash photolysis. Bimolecular rate constants for energy and electron transfer between anthracene and azulene have been measured; kinetic analysis of the decay of the anthracene triplet state and radical cation show that the kinetic parameters depend on the titania content of the sample and the azulene loading. The rate of energy and electron transfer reactions increases as a function of azulene loading and decreases with increasing titania content in titania–silica mixed oxides. These findings indicate that the observed rate of reaction is determined by the rate of diffusion of anthracene on the titania–silica surfaces, whereas, in contrast, the observed rate of reaction on silica gel is predominantly governed by the rate of diffusion of azulene.Graphic abstract

Multi-Electron Oxidation of Anthracene Derivatives by Nonheme Manganese(IV)-Oxo Complexes.

Six-electron oxidation of anthracene to anthraquinone by a nonheme MnIV -oxo complex, [(Bn-TPEN)MnIV (O)]2+ , proceeds through a rate-determining electron transfer from anthracene to [(Bn-TPEN)MnIV (O)]2+ , followed by subsequent fast oxidation reactions to give anthraquinone. The reduced MnII complex ([(Bn-TPEN)MnII ]2+ ) is oxidized by [(Bn-TPEN)MnIV (O)]2+ rapidly to produce the μ-oxo dimer ([(Bn-TPEN)MnIII -O-MnIII (Bn-TPEN)]4+ ). The oxygen atoms of the anthraquinone product were found to derive from the manganese-oxo species by the 18 O-labelling experiments. In the presence of Sc3+ ion, formation of an anthracene radical cation was directly detected in the electron transfer from anthracene to a Sc3+ ion-bound MnIV (O) complex, [(Bn-TPEN)MnIV (O)-(Sc(OTf)3 )2 ]2+ , followed by subsequent further oxidation to yield anthraquinone. When anthracene was replaced by 9,10-dimethylanthracene, electron transfer from 9,10-dimethylanthracene to [(Bn-TPEN)MnIV (O)-(Sc(OTf)3 )2 ]2+ occurred rapidly to produce stable 9,10-dimethylanthracene radical cation. The driving force dependence of the rate constants of electron transfer from the anthracene derivatives to [(Bn-TPEN)MnIV (O)]2+ and [(Bn-TPEN)MnIV (O)-(Sc(OTf)3 )2 ]2+ was well-evaluated in light of the Marcus theory of electron transfer.

Multisurface multimode molecular dynamical simulation of naphthalene and anthracene radical cations by using nearly linear scalable time-dependent discrete variable representation method.

The major portion of the algorithm of the time-dependent discrete variable representation (TDDVR) method is recently parallelized using the shared-memory parallelization scheme with the aim of performing dynamics on relatively large molecular systems. Because of the astronomical importance of naphthalene and anthracene, we have investigated their radical cations as models for theoretical simulation of complex photoelectron spectra and nonradiative decay process using the newly implemented parallel TDDVR code. The strong vibronic coupling among the six lowest doublet electronic states makes these polynuclear hydrocarbons dynamically important. The aim of the present investigation is to show the efficiency of our current TDDVR algorithm to perform dynamics on large dimensional quantum systems in vibronically coupled electronic manifold. Both the sequential and the parallelized TDDVR algorithms are almost linear scalable for an increase in number of processors. Because a significant speed-up is achieved by cycling in the correct way over arrays, all of the simulations are performed within a reasonable wall clock time. Our theoretical spectra well reproduce the features of the corresponding experimental analog. The dynamical outcomes, for example, population, photoelectron spectra, and diffused interstellar bands, etc., of our quantum-classical approach show good agreement with the findings of the well-established quantum dynamical method, that is, multi configuration time-dependent Hartree (MCTDH) approach.

Dissociation of the anthracene radical cation: a comparative look at iPEPICO and collision-induced dissociation mass spectrometry results.

The dissociation of the anthracene radical cation has been studied using two different methods: imaging photoelectron photoion coincidence spectrometry (iPEPCO) and atmospheric pressure chemical ionization-collision induced dissociation mass spectrometry (APCI-CID). Four reactions were investigated: (R1) C14H10(+•) → C14H9(+) + H, (R2) C14H9(+) → C14H8(+•) + H, (R3) C14H10(+•) → C12H8(+•) + C2H2 and (R4) C14H10(+•) → C10H8(+•) + C4H2. An attempt was made to assign structures to each fragment ion, and although there is still room for debate whether for the C12H8(+•) fragment ion is a cyclobuta[b]naphthalene or a biphenylene cation, our modeling results and calculations appear to suggest the more likely structure is cyclobuta[b]naphthalene. The results from the iPEPICO fitting of the dissociation of ionized anthracene are E0 = 4.28 ± 0.30 eV (R1), 2.71 ± 0.20 eV (R2), and 4.20 ± 0.30 eV (average of reaction R3) whereas the Δ(‡)S values (in J K(-1) mol(-1)) are 12 ± 15 (R1), 0 ± 15 (R2), and either 7 ± 10 (using cyclobuta[b]naphthalene ion fragment in reaction R3) or 22 ± 10 (using the biphenylene ion fragment in reaction R3). Modeling of the APCI-CID breakdown diagrams required an estimate of the postcollision internal energy distribution, which was arbitrarily assumed to correspond to a Boltzmann distribution in this study. One goal of this work was to determine if this assumption yields satisfactory energetics in agreement with the more constrained and theoretically vetted iPEPICO results. In the end, it did, with the APCI-CID results being similar.

A multilayer MCTDH study on the full dimensional vibronic dynamics of naphthalene and anthracene cations

Employing the multilayer multiconfiguration time-dependent Hartree (ML-MCTDH) method in conjunction with the multistate multimode vibronic coupling Hamiltonian model, we perform a full dimensional quantum dynamical study on the naphthalene (48D) and anthracene (66D) radical cations in their six lowest-lying doublet electronic states. For easily comparing results of full and reduced dimensionalities, MCTDH simulations based on larger sizes of primitive basis functions and single-particle functions than the previous ones [S. Ghanta, V. S. Reddy, and S. Mahapatra, Phys. Chem. Chem. Phys. 13, 14531 (2011)], are also performed. Extensive ML-MCTDH test calculations are performed to find appropriate ML separations of the wave functions (so-called ML-trees), and the convergence of the dynamical calculations are carefully checked. The ML-MCTDH method was developed for efficiently simulating quantum dynamics of large systems, and in fact the full dimensional ML-MCTDH calculations save a considerable amount of CPU-time in comparison with corresponding reduced dimensional MCTDH simulations. On basis of the present full and reduced dimensional simulations, the photoelectron (PE) spectra of these two cations are simulated and compared with corresponding experimental spectra. The agreement between theoretical and experimental PE spectra is good. Both full and reduced dimensional simulations give all main bands in the PE spectra. The vibronic energy-level positions from both ML-MCTDH and MCTDH calculations agree with corresponding experimental results. These quantum dynamical studies also complement the observations on diffuse interstellar bands with the wavelength of ~7088, ~6707, ~6490, ~6120, and ~5959 Å measured by astronomers as well as laboratory experimentalists.

INFRARED SPECTROSCOPY OF GAS-PHASE POLYCYCLIC AROMATIC HYDROCARBON CATIONS IN THE 10–50 μm SPECTRAL RANGE

The gas-phase infrared spectra of four polycyclic aromatic hydrocarbon (PAH) cations have been recorded in the 10–50 μm (or 1000–200 cm−1) spectral range via IR multiple photon dissociation (IRMPD) spectroscopy. Ionized PAHs are formed by UV laser ionization in an effusive beam and subsequently irradiated with a single pulse of narrowband tunable infrared light produced by the Free-Electron Laser for IntraCavity Experiments FELICE. The ion population is then analyzed in a time-of-flight mass spectrometer. Upon resonance, dissociation is induced so that IR spectra can be recorded by monitoring either the depleted parent ion intensity or the appearance of fragment ions as a function of the wavelength. The intracavity IR fluence enables the recording of IRMPD spectra of strongly bound PAH cations in the hitherto inaccessible far-IR spectral range. Experimental spectra are presented for the radical cations of anthracene, tetracene, pentacene, and coronene. Spectra calculated with density functional theory at the B3LYP/6-311g(2df,2pd) level reproduce IR frequencies reasonably accurately in this spectral range when a uniform scaling factor of 0.94 over the complete 10–50 μm spectral range is employed. We show that even vibrational modes with a calculated IR intensity lower than 1 km mol−1 can be observed. For the catacondensed PAH cations we find CH out-of-plane bending vibrations involving four adjacent CH groups within a few wavenumbers of 733 cm−1, closely matching the 13.6 μm UIR band. For the larger systems, pentacene and coronene, we observe a continuous structureless background absorption above 400 cm−1 which is attributed to the high density of IR dipole allowed combination modes for these systems.

A combined EPR and DFT study of the overcrowded aromatic radical cations from Friedel–Crafts alkylation reactions

► The polycyclic aromatic radical cations were investigated by EPR and ENDOR. ► The aromatic rings in both PAHs radical cations twist out of co-planarity. ► The theoretical hfcc support the experimental assignment of the observed radicals. Electron paramagnetic resonance and electron–nuclear double resonance methods were used to study the polycyclic aromatic radical cations produced in a Friedel–Crafts alkylating system, and the following radical cations were indentified: 3,6,11,14-tetramethyl dibenzo (a, c) triphylene and 2,6-dimethyl-9,10-di(p-methylbenzyl) anthracene radical cations. The results indicate that the observed electron paramagnetic resonance spectra are due to overcrowded polycyclic aromatic radical cations formed from the parent hydrocarbons. It is suggested that benzyl halides produced in the Friedel–Crafts alkylation reactions undergo Scholl condensation to give polycyclic aromatic hydrocarbons, which are converted into corresponding polycyclic aromatic radical cations in the presence of AlCl 3 . We carried out the theoretical calculation of the isotropic 1 H hyperfine coupling constants for studied both PAHs radical cations. The results indicate that the IEFPCM–DFT calculation at B3LYP level with 6-31++G(d,p), EPRII and EPRIII basis sets could well support the experimental hfcc assignment of the observed radicals. Optimized geometry indicates that the aromatic rings in both PAHs radical cations twisted significantly out of co-planarity.

Theoretical study of electronically excited radical cations of naphthalene and anthracene as archetypal models for astrophysical observations. Part I. Static aspects

Motivated by the recent discovery of new diffuse interstellar bands and results from laboratory experiments, ab initio quantum chemistry calculations are carried out for the lowest six electronic states of naphthalene and anthracene radical cations. The calculated adiabatic electronic energies are utilized to construct suitable diabatic electronic Hamiltonians in order to perform nuclear dynamics studies in Part II. Complex entanglement of the electronic states is established for both the radical cations and the coupling surfaces among them are also derived in accordance with the symmetry selection rules. Critical examination of the coupling parameters of the Hamiltonian suggests that 29 (out of 48) and 31 (out of 66) vibrational modes are relevant in the nuclear dynamics in the six lowest electronic states of naphthalene and anthracene radical cations, respectively.

Theoretical study of the electronically excited radical cations of naphthalene and anthracene as archetypal models for astrophysical observations. Part II. Dynamics consequences

Nuclear dynamics is investigated theoretically from first principles by employing the ab initio vibronic models of the prototypical naphthalene and anthracene radical cations developed in Part I. This Part is primarily aimed at corroborating a large amount of available experimental data with a specific final goal to establish an unambiguous link with the current observations in astrophysics and astronomy. The detailed analyses presented here perhaps establish that these two prototypical polycyclic aromatic hydrocarbon radical cations are indeed potential carriers of the observed diffuse interstellar bands.

ChemInform Abstract: Products of the Reactions Between Substituted Anthracene Radical Cations and Nitrogen-Centered Nucleophiles.

ChemInform Abstract: Products of the Reactions Between Substituted Anthracene Radical Cations and Nitrogen-Centered Nucleophiles.

First Principles Quantum Dynamical Investigation Provides Evidence for the Role of Polycyclic Aromatic Hydrocarbon Radical Cations in Interstellar Physics

Inspired by the recent astronomical discovery of new diffused interstellar bands (DIBs) assigned to the electronic transitions in the naphthalene radical cation based on complementary laboratory measurements, we attempt here an ab initio quantum dynamical study to validate this assignment. In addition, the existence and mechanistic details of nonradiative deactivation of electronically excited polycyclic aromatic hydrocarbon (PAH) radical cations in the interstellar medium and their identity as carriers of DIBs are established here focusing on the prototypical naphthalene and anthracene radical cations of the PAH family.

Molecular mechanics-valence bond method for planar conjugated hydrocarbon cations

We present an extension of the molecular mechanics-valence bond (MMVB) hybrid method to study ground and excited states of planar conjugated hydrocarbon cations. Currently, accurate excited state calculations on these systems are limited to expensive ab initio studies of smaller systems: up to 15 active electrons in 16 pi orbitals with complete active space self-consistent field (CASSCF) theory using high symmetry. The new MMVB extension provides a faster, cheaper treatment to investigate larger cation systems with more than 24 active orbitals. Extension requires both new matrix elements and new parameters: In this paper we present both, for the limited planar case. The scheme is tested for the planar radical cations of benzene, naphthalene, anthracene, and phenanthrene. Calculated MMVB relative energies are in good agreement with CASSCF results for equilibrium geometries on the ground and first excited states, and conical intersections.

Reduction of tetranitromethane by electronically excited aromatics in acetonitrile: Spectra and molar absorption coefficients of radical cations of anthracene, phenanthrene and pyrene

Room temperature absorption spectra of the long-lived transient species produced by photolysing solutions containing tetranitromethane (TNM) or a TNM/arene mixture have been recorded with a multi-channel spectrophotometer, capable of μs time resolution and covering a wide spectral range (200–1010 nm). The arene was anthracene ( A), naphthalene ( N), phenanthrene ( Φ), or pyrene ( P). In methanol, A + , N + and Φ + disappear within the available time resolution, but all four cations live for tens or hundreds of μs in acetonitrile; the molar absorption coefficients of A + , Φ + and P + in the latter solvent match those of the respective anions in tetrahydrofuran.