Exploring the chemical dynamics of phenanthrene (C14H10) formation via the bimolecular gas-phase reaction of the phenylethynyl radical (C6H5CC) with benzene (C6H6).

The exploration of the fundamental formation mechanisms of polycyclic aromatic hydrocarbons (PAHs) is crucial for the understanding of molecular mass growth processes leading to two- and three-dimensional carbonaceous nanostructures (nanosheets, graphenes, nanotubes, buckyballs) in extraterrestrial environments (circumstellar envelopes, planetary nebulae, molecular clouds) and combustion systems. While key studies have been conducted exploiting traditional, high-temperature mechanisms such as the hydrogen abstraction-acetylene addition (HACA) and phenyl addition-dehydrocyclization (PAC) pathways, the complexity of extreme environments highlights the necessity of investigating chemically diverse mass growth reaction mechanisms leading to PAHs. Employing the crossed molecular beams technique coupled with electronic structure calculations, we report on the gas-phase synthesis of phenanthrene (C14H10)-a three-ring, 14π benzenoid PAH-via a phenylethynyl addition-cyclization-aromatization mechanism, featuring bimolecular reactions of the phenylethynyl radical (C6H5CC, X2A1) with benzene (C6H6) under single collision conditions. The dynamics involve a phenylethynyl radical addition to benzene without entrance barrier leading eventually to phenanthrene via indirect scattering dynamics through C14H11 intermediates. The barrierless nature of reaction allows rapid access to phenanthrene in low-temperature environments such as cold molecular clouds which can reach temperatures as low as 10 K. This mechanism constitutes a unique, low-temperature framework for the formation of PAHs as building blocks in molecular mass growth processes to carbonaceous nanostructures in extraterrestrial environments thus affording critical insight into the low-temperature hydrocarbon chemistry in our universe.

Differentiating Structurally Similar Fentanyl Analogs by Comparing Density Functional Theory (DFT) Calculations and Surface-Enhanced Raman Spectroscopy (SERS) Results.

Fentanyl and fentanyl analogs are the main cause of recent overdose deaths in the United States. The presence of fentanyl analogs in illicit drugs makes it difficult to estimate their potencies. This makes the detection and differentiation of fentanyl analogs critically significant. Surface-enhanced Raman spectroscopy (SERS) can differentiate structurally similar fentanyl analogs by yielding spectroscopic fingerprints for the detected molecules. In previous years, five fentanyl analogs, carfentanil, furanyl fentanyl, acetyl fentanyl, 4-fluoroisobutyryl fentanyl (4-FIBF), and cyclopropyl fentanyl (CPrF), gained popularity and were found in 76.4% of the fentanyl analogs trafficked. In this study, we focused on 4-FIBF, CPrF, and structurally similar fentanyl analogs. We developed methods to differentiate these fentanyl analogs using theoretical and experimental methods. To do this, a set of fentanyl analogs were examined using density functional theory (DFT) calculations. The DFT results obtained in this project permitted the assignment of spectral bands. These results were then compared with normal Raman and SERS techniques. Structurally similar fentanyl analogs show important differences in their spectra, and they have been visually differentiated from each other both theoretically and experimentally. Additional results using principal component analysis and soft independent modeling of class analogy show they can be distinguished using this technique. The limit of detection values for FIBF and CPrF were determined to be 0.35 ng/mL and 4.4 ng/mL, respectively, using SERS. Experimental results obtained in this project can be readily implemented in field applications and smaller laboratories, where inexpensive portable Raman spectrometers are often present and used in drug analysis.

Transformation of Mercurous [Hg(I)] Species during Laboratory Standard Preparation and Analysis: Implication for Environmental Analysis.

Hg(I) may control Hg redox kinetics; however, its metastable nature hinders analysis. Herein, the stability of Hg(I) during standard preparation and analysis was studied. Gravimetric analysis showed that Hg(I) was stable in its stock solution (1000 mg L-1), yet completely disproportionated when its dilute solution (10 µg L-1) was analyzed using liquid chromatography (LC)-ICPMS. The Hg(I) dimer can form through an energetically favorable comproportionation between Hg(0) and Hg(II), as supported by density functional theory calculation and traced by the rapid isotope exchange between 199Hg(0)aq and 202Hg(II). However, the separation of Hg(0) and Hg(II) (e.g., LC process) triggered its further disproportionation. Polypropylene container, increasing headspace, decreasing pH, and increasing dissolved oxygen significantly enhanced the disproportionation or redox transformations of Hg(I). Thus, using a glass container without headspace and maintaining a slightly alkaline solution are recommended for the dilute Hg(I) stabilization. Notably, we detected elevated concentrations of Hg(I) (4.4-6.1 µg L-1) in creek waters from a heavily Hg-polluted area, accounting for 54-70% of total dissolved Hg. We also verified the reductive formation of Hg(I) in Hg(II)-spiked environmental water samples, where Hg(I) can stably exist in aquatic environments for at least 24 h, especially in seawater. These findings provide mechanistic insights into the transformation of Hg(I), which are indicative of its further environmental identification.

Phenalenyl growth reactions and implications for prenucleation chemistry of aromatics in flames.

The energetics and kinetics of phenalene and phenalenyl growth reactions were studied theoretically. Rate constants of phenalene and phenalenyl H-abstraction and C2H2 addition to the formed radicals were evaluated through quantum-chemical and rate-theory calculations. The obtained values, assigned to all π radicals, were tested in deterministic and kinetic Monte Carlo simulations of aromatics growth under conditions of laminar premixed flames. Kekulé and non-Kekulé structures of the polycyclic aromatic hydrocarbons (PAHs) evolving in the stochastic simulations were identified by on-the-fly constrained optimization. The numerical results demonstrated an increased PAH growth and qualitatively reproduced experimental observations of Homann and co-workers of non-decaying PAH concentrations with nearly equal abundances of even and odd carbon-atom PAHs. The analysis revealed that the PAH growth proceeds via alternating and sterically diverse acetylene and methyl HACA additions. The rapid and diverse spreading in the PAH population supports a nucleation model as PAH dimerization, assisted by the non-equilibrium phenomena, forming planar aromatics first and then transitioning to the PAH-PAH stacking with size.

Methanetriol─Formation of an Impossible Molecule.

Orthocarboxylic acids─organic molecules carrying three hydroxyl groups at the same carbon atom─have been distinguished as vital reactive intermediates by the atmospheric science and physical (organic) chemistry communities as transients in the atmospheric aerosol cycle. Predicted short lifetimes and their tendency to dehydrate to a carboxylic acid, free orthocarboxylic acids, signify one of the most elusive classes of organic reactive intermediates, with even the simplest representative methanetriol (CH(OH)3)─historically known as orthoformic acid─not previously been detected experimentally. Here, we report the first synthesis of the previously elusive methanetriol molecule in low-temperature mixed methanol (CH3OH) and molecular oxygen (O2) ices subjected to energetic irradiation. Supported by electronic structure calculations, methanetriol was identified in the gas phase upon sublimation via isomer-selective photoionization reflectron time-of-flight mass spectrometry combined with isotopic substitution studies and the detection of photoionization fragments. The first synthesis and detection of methanetriol (CH(OH)3) reveals its gas-phase stability as supported by a significant barrier hindering unimolecular decomposition. These findings progress our fundamental understanding of the chemistry and chemical bonding of methanetriol, hydroxyperoxymethane (CH3OOOH), and hydroxyperoxymethanol (CH2(OH)OOH), which are all prototype molecules in the oxidation chemistry of the atmosphere.

Elucidating the chemical dynamics of the elementary reactions of the 1-propynyl radical (CH3CC; X2A1) with 2-methylpropene ((CH3)2CCH2; X1A1).

Exploiting the crossed molecular beam technique, we studied the reaction of the 1-propynyl radical (CH3CC; X2A1) with 2-methylpropene (isobutylene; (CH3)2CCH2; X1A1) at a collision energy of 38 ± 3 kJ mol-1. The experimental results along with ab initio and statistical calculations revealed that the reaction has no entrance barrier and proceeds via indirect scattering dynamics involving C7H11 intermediates with lifetimes longer than their rotation period(s). The reaction is initiated by the addition of the 1-propynyl radical with its radical center to the π-electron density at the C1 and/or C2 position in 2-methylpropene. Further, the C7H11 intermediate formed from the C1 addition either emits atomic hydrogen or undergoes isomerization via [1,2-H] shift from the CH3 or CH2 group prior to atomic hydrogen loss preferentially leading to 1,2,4-trimethylvinylacetylene (2-methylhex-2-en-4-yne) as the dominant product. The molecular structures of the collisional complexes promote hydrogen atom loss channels. RRKM results show that hydrogen elimination channels dominate in this reaction, with a branching ratio exceeding 70%. Since the reaction of the 1-propynyl radical with 2-methylpropene has no entrance barrier, is exoergic, and all transition states involved are located below the energy of the separated reactants, bimolecular collisions are feasible to form trimethylsubstituted 1,3-enyne (p1) via a single collision event even at temperatures as low as 10 K prevailing in cold molecular clouds such as G+0.693. The formation of trimethylsubstituted vinylacetylene could serve as the starting point of fundamental molecular mass growth processes leading to di- and trimethylsubstituted naphthalenes via the HAVA mechanism.

One Collision-Two Substituents: Gas-Phase Preparation of Xylenes under Single-Collision Conditions.

The fundamental reaction pathways to the simplest dialkylsubstituted aromatics-xylenes (C6 H4 (CH3 )2 )-in high-temperature combustion flames and in low-temperature extraterrestrial environments are still unknown, but critical to understand the chemistry and molecular mass growth processes in these extreme environments. Exploiting crossed molecular beam experiments augmented by state-of-the-art electronic structure and statistical calculations, this study uncovers a previously elusive, facile gas-phase synthesis of xylenes through an isomer-selective reaction of 1-propynyl (methylethynyl, CH3 CC) with 2-methyl-1,3-butadiene (isoprene, C5 H8 ). The reaction dynamics are driven by a barrierless addition of the radical to the diene moiety of 2-methyl-1,3-butadiene followed by extensive isomerization (hydrogen shifts, cyclization) prior to unimolecular decomposition accompanied by aromatization via atomic hydrogen loss. This overall exoergic reaction affords a preparation of xylenes not only in high-temperature environments such as in combustion flames and around circumstellar envelopes of carbon-rich Asymptotic Giant Branch (AGB) stars, but also in low-temperature cold molecular clouds (10 K) and in hydrocarbon-rich atmospheres of planets and their moons such as Triton and Titan. Our study established a hitherto unknown gas-phase route to xylenes and potentially more complex, disubstituted benzenes via a single collision event highlighting the significance of an alkyl-substituted ethynyl-mediated preparation of aromatic molecules in our Universe.

Plasmon-mediated dehydrogenation of the aromatic methyl group and benzyl radical formation.

Plasmonic molecular junctions can harvest visible light and effectively catalyze chemical reactions. The strong light field concentrated in the plasmonic junction also enables the application of surface enhanced Raman spectroscopy (SERS) to probe the catalyzed chemical reactions in situ and in real time down to single-molecule resolution. The benzyl radical produced from the aromatic methyl group through the dehydrogenation reaction is an important precursor for a large variety of reactions. Here, we used time-resolved SERS to conduct a mechanistic study of the plasmon-driven dehydrogenation reaction of the aromatic methyl group under ambient conditions under the illumination of red light on the apex of a gold nanoelectrode. Transient spectral changes with intensity bursts are frequently observed. Based on density functional theory and picocavity based local electric field enhancement calculations, they result from the plasmon mediated dehydrogenation reaction of aromatic methyl groups. The dehydrogenation reaction produces a benzyl radical, which is consequently converted to a benzyl anion. The benzyl anion is stabilized through strong interactions with gold, leading to the formation of dynamic gold adatoms and picocavities. In addition to the benzyl anion, we found spectral evidence that the benzyl radical generates dimers through a self-reaction. Furthermore, we demonstrated that the dehydrogenation reaction could be facially modulated by changing the electrode potential, which is attributed to the modulated inductive effect.

Gas-phase formation of the resonantly stabilized 1-indenyl (C9H7•) radical in the interstellar medium.

The 1-indenyl (C9H7•) radical, a prototype aromatic and resonantly stabilized free radical carrying a six- and a five-membered ring, has emerged as a fundamental molecular building block of nonplanar polycyclic aromatic hydrocarbons (PAHs) and carbonaceous nanostructures in deep space and combustion systems. However, the underlying formation mechanisms have remained elusive. Here, we reveal an unconventional low-temperature gas-phase formation of 1-indenyl via barrierless ring annulation involving reactions of atomic carbon [C(3P)] with styrene (C6H5C2H3) and propargyl (C3H3•) with phenyl (C6H5•). Macroscopic environments like molecular clouds act as natural low-temperature laboratories, where rapid molecular mass growth to 1-indenyl and subsequently complex PAHs involving vinyl side-chained aromatics and aryl radicals can occur. These reactions may account for the formation of PAHs and their derivatives in the interstellar medium and carbonaceous chondrites and could close the gap of timescales of their production and destruction in our carbonaceous universe.

Gas-phase preparation of azulene (C10H8) and naphthalene (C10H8) via the reaction of the resonantly stabilized fulvenallenyl and propargyl radicals.

Synthetic routes to the 10π Hückel aromatic azulene (C10H8) molecule, the simplest polycyclic aromatic hydrocarbon carrying an adjacent five- and seven-membered ring, have been of fundamental importance due to the role of azulene - a structural isomer of naphthalene - as an essential molecular building block of saddle-shaped carbonaceous nanostructures such as curved nanographenes and nanoribbons. Here, we report on the very first gas phase preparation of azulene by probing the gas-phase reaction between two resonantly stabilized radicals, fulvenallenyl and propargyl , in a molecular beam through isomer-resolved vacuum ultraviolet photoionization mass spectrometry. Augmented by electronic structure calculations, the novel Fulvenallenyl Addition Cyclization Aromatization (FACA) reaction mechanism affords a versatile concept for introducing the azulene moiety into polycyclic aromatic systems thus facilitating an understanding of barrierless molecular mass growth processes of saddle-shaped aromatics and eventually carbonaceous nanoparticles (soot, interstellar grains) in our universe.

Gas-Phase Synthesis of Coronene through Stepwise Directed Ring Annulation.

Molecular beam experiments together with electronic structure calculations provide the first evidence of a complex network of elementary gas-phase reactions culminating in the bottom-up preparation of the 24π aromatic coronene (C24H12) molecule─a representative peri-fused polycyclic aromatic hydrocarbon (PAH) central to the complex chemistry of combustion systems and circumstellar envelopes of carbon stars. The gas-phase synthesis of coronene proceeds via aryl radical-mediated ring annulations through benzo[e]pyrene (C20H12) and benzo[ghi]perylene (C22H12) involving armchair-, zigzag-, and arm-zig-edged aromatic intermediates, highlighting the chemical diversity of molecular mass growth processes to polycyclic aromatic hydrocarbons. The isomer-selective identification of five- to six-ringed aromatics culminating with the detection of coronene is accomplished through photoionization and is based upon photoionization efficiency curves along with photoion mass-selected threshold photoelectron spectra, providing a versatile concept of molecular mass growth processes via aromatic and resonantly stabilized free radical intermediates to two-dimensional carbonaceous nanostructures.

Exploring the Chemical Dynamics of Phenylethynyl Radical (C6H5CC; X2A1) Reactions with Allene (H2CCCH2; X1A1) and Methylacetylene (CH3CCH; X1A1).

The bimolecular gas-phase reactions of the phenylethynyl radical (C6H5CC, X2A1) with allene (H2CCCH2), allene-d4 (D2CCCD2), and methylacetylene (CH3CCH) were studied under single-collision conditions utilizing the crossed molecular beams technique and merged with electronic structure and statistical calculations. The phenylethynyl radical was found to add without an entrance barrier to the C1 carbon of the allene and methylacetylene reactants, resulting in doublet C11H9 collision complexes with lifetimes longer than their rotational periods. These intermediates underwent unimolecular decomposition via atomic hydrogen loss through tight exit transition states in facile radical addition─hydrogen atom elimination mechanisms forming predominantly 3,4-pentadien-1-yn-1-ylbenzene (C6H5CCCHCCH2) and 1-phenyl-1,3-pentadiyne (C6H5CCCCCH3) in overall exoergic reactions (-110 kJ mol-1 and -130 kJ mol-1) for the phenylethynyl-allene and phenylethynyl-methylacetylene systems, respectively. These barrierless reaction mechanisms mirror those of the ethynyl radical (C2H, X2Σ+) with allene and methylacetylene forming predominantly ethynylallene (HCCCHCCH2) and methyldiacetylene (HCCCCCH3), respectively, suggesting that in the aforementioned reactions the phenyl group acts as a spectator. These molecular mass growth processes are accessible in low-temperature environments such as cold molecular clouds (TMC-1) or Saturn's moon Titan, efficiently incorporating a benzene ring into unsaturated hydrocarbons.

Synthesis of interstellar propen-2-ol (CH3C(OH)CH2) - the simplest enol tautomer of a ketone.

Enols - tautomers of ketones or aldehydes - are anticipated to be ubiquitous in the interstellar medium and play a key role in the formation of complex organic molecules in deep space, but their fundamental formation mechanisms have remained largely elusive as of now. Here we present a combined experimental and computational study demonstrating the first preparation of propen-2-ol (CH3C(OH)CH2) and its isomer methyl vinyl ether (CH3OCHCH2) in low-temperature acetone (CH3COCH3) ices upon exposure to energetic electrons. Propen-2-ol is the simplest enol tautomer of a ketone. Exploiting tunable vacuum ultraviolet photoionization in conjunction with reflectron time-of-flight mass spectrometry, propen-2-ol and methyl vinyl ether were monitored in the gas phase upon sublimation during the temperature-programmed desorption process suggesting that both isomers are promising candidates for future astronomical searches such as via the James Webb Space Telescope. Electronic structure calculations reveal that the barrier of keto-enol tautomerization can be reduced by more than a factor of two (162 kJ mol-1) through the involvement of solvating water molecules under realistic conditions on interstellar grains. The implicit solvent effects, i.e., the influences of the solvent dipole field on the barrier height are found to be minimal and do not exceed 10 kJ mol-1. Our findings signify a crucial step toward a better understanding of the enolization of ketones in the interstellar medium thus constraining the molecular structures and complexity of molecules that form in extraterrestrial ices - ketones - through non-equilibrium chemistry.

Quantum Tunneling Mediated Low-Temperature Synthesis of Interstellar Hemiacetals.

Sugars and sugar-related molecules are ubiquitous in carbonaceous meteorites and in star-forming regions, but the underlying mechanisms of their formation have remained largely elusive. Herein, we report an unconventional synthesis of the hemiacetal, (R/S)-1-methoxyethanol (CH3OCH(OH)CH3), through quantum tunneling mediated reactions in low-temperature interstellar model ices composed of acetaldehyde (CH3CHO) and methanol (CH3OH). The detection of racemic 1-methoxyethanol through a bottom-up synthesis from simple, abundant precursor molecules within interstellar ices represents a vital starting point to the formation of complex interstellar hemiacetals. Once synthesized, hemiacetals may act as possible precursors to interstellar sugars and sugar-related molecules in deep space.

Unconventional gas-phase preparation of the prototype polycyclic aromatic hydrocarbon naphthalene (C10H8) via the reaction of benzyl (C7H7) and propargyl (C3H3) radicals coupled with hydrogen-atom assisted isomerization.

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous in the interstellar medium and in meteorites such as Murchison and Allende and signify the missing link between resonantly stabilized free radicals and carbonaceous nanoparticles (soot particles, interstellar grains). However, the predicted lifetime of interstellar PAHs of some 108 years imply that PAHs should not exist in extraterrestrial environments suggesting that key mechanisms of their formation are elusive. Exploiting a microchemical reactor and coupling these data with computational fluid dynamics (CFD) simulations and kinetic modeling, we reveal through an isomer selective product detection that the reaction of the resonantly stabilized benzyl and the propargyl radicals synthesizes the simplest representative of PAHs - the 10π Hückel aromatic naphthalene (C10H8) molecule - via the novel Propargyl Addition-BenzAnnulation (PABA) mechanism. The gas-phase preparation of naphthalene affords a versatile concept of the reaction of combustion and astronomically abundant propargyl radicals with aromatic radicals carrying the radical center at the methylene moiety as a previously passed over source of aromatics in high temperature environments thus bringing us closer to an understanding of the aromatic universe we live in.

Gas phase synthesis of the C40 nano bowl C40H10.

Nanobowls represent vital molecular building blocks of end-capped nanotubes and fullerenes detected in combustion systems and in deep space such as toward the planetary nebula TC-1, but their fundamental formation mechanisms have remained elusive. By merging molecular beam experiments with electronic structure calculations, we reveal a complex chain of reactions initiated through the gas-phase preparation of benzocorannulene (C24H12) via ring annulation of the corannulenyl radical (C20H9•) by vinylacetylene (C4H4) as identified isomer-selectively in situ via photoionization efficiency curves and photoion mass-selected threshold photoelectron spectra. In silico studies provided compelling evidence that the benzannulation mechanism can be expanded to pentabenzocorannulene (C40H20) followed by successive cyclodehydrogenation to the C40 nanobowl (C40H10) - a fundamental building block of buckminsterfullerene (C60). This high-temperature pathway opens up isomer-selective routes to nanobowls via resonantly stabilized free-radical intermediates and ring annulation in circumstellar envelopes of carbon stars and planetary nebulae as their descendants eventually altering our insights of the complex chemistry of carbon in our Galaxy.

Radical-Radical Reactions in Molecular Weight Growth: The Phenyl + Propargyl Reaction.

The mechanism for hydrocarbon ring growth in sooting environments is still the subject of considerable debate. The reaction of phenyl radical (C6H5) with propargyl radical (H2CCCH) provides an important prototype for radical-radical ring-growth pathways. We studied this reaction experimentally over the temperature range of 300-1000 K and pressure range of 4-10 Torr using time-resolved multiplexed photoionization mass spectrometry. We detect both the C9H8 and C9H7 + H product channels and report experimental isomer-resolved product branching fractions for the C9H8 product. We compare these experiments to theoretical kinetics predictions from a recently published study augmented by new calculations. These ab initio transition state theory-based master equation calculations employ high-quality potential energy surfaces, conventional transition state theory for the tight transition states, and direct CASPT2-based variable reaction coordinate transition state theory (VRC-TST) for the barrierless channels. At 300 K only the direct adducts from radical-radical addition are observed, with good agreement between experimental and theoretical branching fractions, supporting the VRC-TST calculations of the barrierless entrance channel. As the temperature is increased to 1000 K we observe two additional isomers, including indene, a two-ring polycyclic aromatic hydrocarbon, and a small amount of bimolecular products C9H7 + H. Our calculated branching fractions for the phenyl + propargyl reaction predict significantly less indene than observed experimentally. We present further calculations and experimental evidence that the most likely cause of this discrepancy is the contribution of H atom reactions, both H + indenyl (C9H7) recombination to indene and H-assisted isomerization that converts less stable C9H8 isomers into indene. Especially at low pressures typical of laboratory investigations, H-atom-assisted isomerization needs to be considered. Regardless, the experimental observation of indene demonstrates that the title reaction leads, either directly or indirectly, to the formation of the second ring in polycyclic aromatic hydrocarbons.

Anticancer Drug Doxorubicin Spontaneously Reacts with GTP and dGTP.

Here, we reported a spontaneous reaction between anticancer drug doxorubicin and GTP or dGTP. Incubation of doxorubicin with GTP or dGTP at 37 °C or above yields a covalent product: the doxorubicin-GTP or -dGTP conjugate where a covalent bond is formed between the C14 position of doxorubicin and the 2-amino group of guanine. Density functional theory calculations show the feasibility of this spontaneous reaction. Fluorescence imaging studies demonstrate that the doxorubicin-GTP and -dGTP conjugates cannot enter nuclei although they rapidly accumulate in human SK-OV-3 and NCI/ADR-RES cells. Consequently, the doxorubicin-GTP and -dGTP conjugates are less cytotoxic than doxorubicin. We also demonstrate that doxorubicin binds to ATP, GTP, and other nucleotides with a dissociation constant (Kd) in the sub-millimolar range. Since human cells contain millimolar levels of ATP and GTP, these results suggest that doxorubicin may target ATP and GTP, energy molecules that support essential processes in living organisms.

Gas-phase detection of oxirene.

Oxirenes-highly strained 4π Hückel antiaromatic organics-have been recognized as key reactive intermediates in the Wolff rearrangement and in interstellar environments. Predicting short lifetimes and tendency toward ring opening, oxirenes are one of the most mysterious classes of organic transients, with the isolation of oxirene (c-C2H2O) having remained elusive. Here, we report on the preparation of oxirene in low-temperature methanol-acetaldehyde matrices upon energetic processing through isomerization of ketene (H2CCO) followed by resonant energy transfer of the internal energy of oxirene to the vibrational modes (hydroxyl stretching and bending, methyl deformation) of methanol. Oxirene was detected upon sublimation in the gas phase exploiting soft photoionization coupled with a reflectron time-of-flight mass spectrometry. These findings advance our fundamental understanding of the chemical bonding and stability of cyclic, strained molecules and afford a versatile strategy for the synthesis of highly ring-strained transients in extreme environments.

Exotic Reaction Dynamics in the Gas-Phase Preparation of Anthracene (C14H10) via Spiroaromatic Radical Transients in the Indenyl-Cyclopentadienyl Radical-Radical Reaction.

The gas-phase reaction between the 1-indenyl (C9H7•) radical and the cyclopentadienyl (C5H5•) radical has been investigated for the first time using synchrotron-based mass spectrometry coupled with a pyrolytic reactor. Soft photoionization with tunable vacuum ultraviolet photons afforded for the isomer-selective identification of the production of phenanthrene, anthracene, and benzofulvalene (C14H10). The classical theory prevalent in the literature proposing that radicals combine only at their specific radical centers is challenged by our discovery of an unusual reaction pathway that involves a barrierless combination of a resonantly stabilized hydrocarbon radical with an aromatic radical at the carbon atom adjacent to the traditional C1 radical center; this unconventional addition is followed by substantial isomerization into phenanthrene and anthracene via a category of exotic spiroaromatic intermediates. This result leads to a deeper understanding of the evolution of the cosmic carbon budget and provides new methodologies for the bottom-up synthesis of unique spiroaromatics that may be relevant for the synthesis of more complex aromatic carbon skeletons in deep space.