A theoretical study on the photochemical generation of phenylborylene from phenyldiazidoborane

Mu, Di; Li, Quan-Song

doi:10.1039/d2cp05349g

Cited by 4 publications

(3 citation statements)

References 56 publications

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“…Intrinsic reaction coordinate (IRC) 32,33 calculations are carried out to ensure that the transition states indeed connect with appropriate reactants and products. 34,35 All of these electronic structure calculations are carried out in the Gaussian 16 package. 36 The search for MECPs is conducted using a modified version of Harvey's code 37 (sobMECP 38 ) interfaced with Gaussian 16.…”

Section: Qm/mm Modelmentioning

confidence: 99%

The origin of [2+2] photocycloaddition reaction in the solid state driving ACQ-to-AIE transformation

Wei,

Zhu,

et al. 2024

J. Mater. Chem. C

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Section: Qm/mm Modelmentioning

confidence: 99%

The origin of [2+2] photocycloaddition reaction in the solid state driving ACQ-to-AIE transformation

Wei,

Zhu,

et al. 2024

J. Mater. Chem. C

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“…One-dimensional potential energy surfaces that are represented in Figure for the dissociation reactions of E -NNOH+ and N(H + )NO, are built with the linear interpolation method, − and their electronic energies are calculated with the MS-CASPT2 approximation from the appropriated CASSCF reference wave function, a method that has been well established to study reaction mechanisms, especially, dissociation reactions. − …”

Section: Computational Detailsmentioning

confidence: 99%

Identification of the Photoreactive Species of Protonated N-Nitrosopiperidine in Acid Medium: A CASPT2 and DFT Study

Soto

2023

J. Phys. Chem. A

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In this work, we have studied the initial reaction step after photoexcitation of protonated N-nitrosopiperidine both in the gas and condensed phases. To achieve this end, we have applied the CASPT2 and MP2 wave function methods and the density functional theory approach. It is found that the site of protonation of N-nitrosopiperidine in acid medium depends on the solvent: protonation occurs at the oxygen atom in protic solvents, while in aprotic solvents, the proton is bonded at the N-atom of the amine moiety. Furthermore, protonation at such an N-atom is the unique protonated species that absorbs in the visible range and directly dissociates into aminium radical cation and nitric oxide.

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“…Several theoretical studies on the PC reactions of AIEgens have stirred up extensive discussions. − Nakamura and colleagues studied the mechanism of the ring-closing reaction of 1,2-bis(3-thienyl)ethylene by calculating the conical intersection (CI) between the ground state (S 0 ) and the first excited state (S 1 ) . Su et al proposed that the PC reaction of diarylethene derivatives may occur in the excited state by scanning the potential energy surface of DAE PC by the TD-DFT method .…”

Section: Introductionmentioning

confidence: 99%

Theoretical Study of the Photocyclization Reaction-Induced Dual Aggregation-Induced Emission Phenomenon

Yang,

Wei,

et al. 2023

J. Phys. Chem. A

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Photochromic molecules with aggregation-induced emission (AIE) effects are of great value and prospective in various practical applications. To explore its inherent mechanism, the open isomer ap-BBTE and the closed isomer c-BBTE were chosen to perform the theoretical calculation using the quantum mechanics/ molecular mechanics model combined with thermal vibration correlation function formalism. The calculations show that the photocyclization (PC) reaction from ap-BBTE to c-BBTE facilitates an improvement in the AIE effect. It is found that the fluorescence quantum yield (Φ F ) enhancement of ap-BBTE is attributed to the restriction of the low-frequency rotational motion of the benzothiophene moiety and the high-frequency stretching vibrations of the C−C bond between the benzothiophene and benzylbis(thiadiazole) vinyl groups after aggregation. For c-BBTE, the increase in Φ F upon aggregation is mainly due to the suppression of the high-frequency stretching vibration of the C−C bond between the benzothiophene and the benzobis(thiadiazole) vinyl groups. In addition, the AIE effect was also enhanced from ap-BBTE to c-BBTE, which is consistent with the experimental phenomenon. The corresponding emission spectrum red-shifted from ap-BBTE to c-BBTE in both dilute solution and the crystalline state due to the improved intramolecular conjugation of c-BBTE. Moreover, the PC reaction from ap-BBTE to c-BBTE easily occurs in an excited state with a low energy barrier transition state by forming a C−C bond between benzothiophene groups effectively in dilute solution. Our calculations provide theoretical guidance for the further rational design of efficient AIE luminogens.

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A theoretical study on the photochemical generation of phenylborylene from phenyldiazidoborane

Abstract: Organic borylenes are a kind of highly reactive species, which play important roles in lots of reactions as vigorous intermediates. In this work, we investigated the photochemical generation mechanisms of...

Cited by 4 publications

References 56 publications

The origin of [2+2] photocycloaddition reaction in the solid state driving ACQ-to-AIE transformation

The origin of [2+2] photocycloaddition reaction in the solid state driving ACQ-to-AIE transformation

Identification of the Photoreactive Species of Protonated N-Nitrosopiperidine in Acid Medium: A CASPT2 and DFT Study

Theoretical Study of the Photocyclization Reaction-Induced Dual Aggregation-Induced Emission Phenomenon

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