Decomposition of Gaseous Phthalic Anhydride from a Vibrationally Hot Molecule Formed by ArF Laser Irradiation

Yatsuhashi, Tomoyuki; Nakashima, Nobuaki

doi:10.1021/jp992469q

Cited by 10 publications

(4 citation statements)

References 34 publications

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“…In the case of the HPA • radical, the process that consists of a simultaneous rupture of two C−CO 2 bonds forming a benzyne biradical (as was described for the photodecomposition of gaseous phthalic anhydride) 34 and a C 2 O 4 H • intermediate requires 3.45 eV from the optimized planar radical structure. This process is thus much too high in energy to be observed.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Loss of CO₂ from Monodeprotonated Phthalic Acid upon Photodissociation and Dissociative Electron Detachment

et al. 2021

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The decarboxylation (CO2 loss) mechanism of cold monodeprotonated phthalic acid was studied in a photodissociation action spectrometer by quantifying mass-selected product anions and neutral particles as a function of the excitation energy. The analysis proceeded by interpreting the translational energy distribution of the generated uncharged products, and with the help of quantum calculations. In particular, this study reveals different fragmentation pathways in the deprotonated anion and in the radical generated upon electron photodetachment. Unlike the behaviour found in other deprotonated aryl carboxylic acids, which do not fragment in the anion excited state, a double loss of CO2 molecules takes place in the phthalic monoanion. Moreover, at higher excitation energies the phthalic monoanion experiences decarboxylative photodetachment with a statistical distribution of product translational energies, which contrasts with the impulsive dissociation reactions characteristic of other aryl carboxylic anions.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Loss of CO₂ from Monodeprotonated Phthalic Acid upon Photodissociation and Dissociative Electron Detachment

et al. 2021

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“…Two different optical arrangements were constructed for obtaining time-resolved absorption spectra and rise curves under collision-free conditions. For the transient absorption spectra measurements, a perpendicular arrangement between monitor beam and the laser beam was used . The optical path length was 3 cm, and the laser beam was irradiated in an area of 0.5 cm × 3.0 cm.…”

Section: Methodsmentioning

confidence: 99%

One- and Two-Photon-Induced Ring-Cleavage Reactions of Strained Benzocycloalkenes via Hot Molecules

2005

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The ring-cleavage reactions of a series of benzocycloalkenes were studied using an ArF excimer laser. Product formation was significantly suppressed in the presence of nitrogen; therefore, the presence of vibrationally excited states (hot molecules), as intermediates, was indicated. The product of highly strained benzocyclobutene was linearly proportional to the laser fluence, whereas those of benzocyclopentene and benzocyclohexene were proportional to the square of the laser fluence in the presence of nitrogen. These phenomena cannot be understood as photochemical bond cleavage in the electronic excited state, but instead appear to be the result of single- and two-photon reactions of hot molecules. The dissociation rate constants were evaluated by a statistical rate theory under the assumption that the reaction occurred from the hot molecule. The reaction rate of highly strained benzocyclobutene was predicted to be faster than the collisional rate with foreign gas, even if it had vibrational energy equivalent to one photon; however, the reaction rates of less strained benzocyclohexene were expected to compete with the collisional rate when the vibrational energy was equivalent to two photons. Benzocyclopentene was an intermediate case and showed both single- and two-photon reactions. The dissociation rate constant of 1.4 x 10(6) s(-1) was successfully obtained from benzocyclopentene under collision-free conditions. This value was in fair agreement with the calculated value. The different dissociation rate constants of the molecules were well-explained in terms of the strain energy. Although the strain energy varies in a wide range (10-130 kJ mol(-1)), the simple model of the calculations reproduced the observed values of the CH2-CH2 bond dissociation in strained benzocycloalkenes.

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“…[25][26][27][28] The selective photolysis and pyrolysis of anhydrides has proven to be a suitable approach for the formation of arynes, as schematically shown in Figure 1a for the case of the phthalic anhydride (PhA). [29][30][31][32][33][34] Many organic synthesis experiments have been carried out in solution, gas-phase and in inert gas matrices at cryogenic temperature. Several phthalic anhydride derivatives were demonstrated to be photochemically active upon UV light irradiation inducing the dissociation of the anhydride group and leading to the loss of CO and CO 2, forming highly reactive arynes that can occasionally di-or trimerize.…”

Section: Introductionmentioning

confidence: 99%

“…The selective photolysis and pyrolysis of anhydrides has proven to be a suitable approach for the formation of arynes, as schematically shown in Figure 1a for the case of the phthalic anhydride (PhA) [29–34] . Many organic synthesis experiments have been carried out in solution, gas‐phase and in inert gas matrices at cryogenic temperature.…”

Section: Introductionmentioning

confidence: 99%

Controlling On‐Surface Photoactivity: The Impact of π‐Conjugation in Anhydride‐Functionalized Molecules on a Semiconductor Surface

Frezza,

Sánchez‐Grande,

Canola

et al. 2024

Angewandte Chemie

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On‐surface synthesis has become a prominent method for growing low‐dimensional carbon‐based nanomaterials on metal surfaces. However, the necessity of decoupling organic nanostructures from metal substrates to exploit their properties requires either transfer methods or new strategies to perform reactions directly on inert surfaces. The use of on‐surface light‐induced reactions directly on semiconductor/insulating surfaces represents an alternative approach to address these challenges. Here, exploring the photochemical activity of different organic molecules on a SnSe semiconductor surface under ultra‐high vacuum, we present a novel on‐surface light‐induced reaction. The selective photodissociation of the anhydride group is observed, releasing CO and CO2. Moreover, we rationalize the relationship between the photochemical activity and the π‐conjugation of the molecular core. The different experimental behaviour of two model anhydrides was elucidated by theoretical calculations, showing how the molecular structure influences the distribution of the excited states. Our findings open new pathways for on‐surface synthesis directly on technologically relevant substrates.

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Decomposition of Gaseous Phthalic Anhydride from a Vibrationally Hot Molecule Formed by ArF Laser Irradiation

Cited by 10 publications

References 34 publications

Loss of CO₂ from Monodeprotonated Phthalic Acid upon Photodissociation and Dissociative Electron Detachment

Loss of CO₂ from Monodeprotonated Phthalic Acid upon Photodissociation and Dissociative Electron Detachment

One- and Two-Photon-Induced Ring-Cleavage Reactions of Strained Benzocycloalkenes via Hot Molecules

Controlling On‐Surface Photoactivity: The Impact of π‐Conjugation in Anhydride‐Functionalized Molecules on a Semiconductor Surface

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Decomposition of Gaseous Phthalic Anhydride from a Vibrationally Hot Molecule Formed by ArF Laser Irradiation

Cited by 10 publications

References 34 publications

Loss of CO2 from Monodeprotonated Phthalic Acid upon Photodissociation and Dissociative Electron Detachment

Loss of CO2 from Monodeprotonated Phthalic Acid upon Photodissociation and Dissociative Electron Detachment

One- and Two-Photon-Induced Ring-Cleavage Reactions of Strained Benzocycloalkenes via Hot Molecules

Controlling On‐Surface Photoactivity: The Impact of π‐Conjugation in Anhydride‐Functionalized Molecules on a Semiconductor Surface

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Loss of CO₂ from Monodeprotonated Phthalic Acid upon Photodissociation and Dissociative Electron Detachment

Loss of CO₂ from Monodeprotonated Phthalic Acid upon Photodissociation and Dissociative Electron Detachment