Regulated stepwise ESDPT mechanism associated with chalcogen substitutions in BDIBD derivatives

Liu, Chang; Zhao, Jinfeng; Chen, Jiahe; Wang, Mingwei; Hou, Mengmeng; Yang, Liang

doi:10.1039/d3cp05837a

Cited by 24 publications

(1 citation statement)

References 65 publications

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“…In addition, the infrared (IR) vibrational spectrum is also a powerful tool for analyzing hydrogen bond strength, which has been widely used in numerous chemical investigations. − As we all know, the red shift or blue shift of the IR vibrational spectrum shows the enhancement or weakening of the hydrogen bond, respectively. Hence, the IR vibrational spectra of the O1–H1 bond for STF, DTF, and TTF in S 0 and S 1 states are simulated in Figure S1 in the Supporting Information.…”

Section: Resultsmentioning

confidence: 99%

Theoretical Insights into the Effect of Different Numbers of Thiophene Groups on Hydrogen Bond Interaction and Excited-State Intramolecular Proton-Transfer Process for Flavonoid Derivatives

Zhou,

Wang,

Cui

et al. 2024

J. Phys. Chem. A

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In this study, we systematically explored the impact of varying the number of thiophene groups on the hydrogen bond interaction and excited-state intramolecular proton-transfer (ESIPT) processes in flavonoid derivatives (STF, DTF, and TTF) using the density functional theory and time-dependent density functional theory methods. Initially, a thorough analysis of the optimized geometric structures revealed that the intramolecular hydrogen bond in the S1 state is enhanced and gradually weakened as the number of thiophene groups increases. To gain a deeper understanding of the hydrogen bond interaction, topological analysis, interaction region indicator scatter plots, and isosurface plots were employed. These images provide further insights that align with the structural analysis. Additionally, we observed a red-shift in the electronic spectra (absorption and fluorescence spectra), which is primarily attributed to the narrowing of the energy gap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital, as elucidated by the frontier molecular orbitals. Furthermore, a combined analysis between the hole–electron distribution and the transition density matrix heat map shows that electron excitation involves the unidirectional charge-transfer mechanism. In the end, by conducting relaxed potential energy curve scans, we found that an increase in the number of thiophene groups elevates the energy barrier for ESIPT, making it more challenging for the reaction. In summary, our study underscores the vital effect of thiophene-substituted numbers in modulating the ESIPT process, which is able to provide valuable insights for the design and synthesis of desired organic fluorescent probes in the future.

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Section: Resultsmentioning

confidence: 99%

Theoretical Insights into the Effect of Different Numbers of Thiophene Groups on Hydrogen Bond Interaction and Excited-State Intramolecular Proton-Transfer Process for Flavonoid Derivatives

Zhou,

Wang,

Cui

et al. 2024

J. Phys. Chem. A

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Deciphering the Differential Origin of Hydrogen Bonds in the Normal and Tautomer Forms of 7‐Azaindole:Piperidin‐2‐one Hydrogen‐Bonded Complex: Excited‐State Double Proton Transfer

Paul

2024

Advcd Theory and Sims

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The excited‐state double proton transfer (ESDPT) reaction in the intermolecular hydrogen‐bonded complex 7‐azaindole:piperidin‐2‐one is investigated by quantum chemical calculations with particular emphasis on the H‐bonding interactions within the system. The natural bond orbital (NBO) calculations show that the X─H···Y H‐bonds in the studied complexes, namely, 7‐azaindole:piperidin‐2‐one (N‐form) and 7H‐pyrrolo[2,3‐b]pyridine:3,4,5,6‐tetrahydropyridin‐2‐ol (T‐form, proton transferred tautomer) are aptly described by hyperconjugative charge transfer effect ( is non‐bonded lone‐pair on Y‐atom). That the hyperconjugation effect outplays the rehybridization effect is invoked to account for the observed red‐shifting H‐bonds in harmony with the Bent's rule. The differential nature of interactions underlying the origin of X─H···Y H‐bonds in the complexes (N‐form and T‐form) is explored from atoms‐in‐molecules (AIM) calculations. The H‐bonds in the N‐form are found to have a primarily electrostatic origin (closed‐shell interaction) whereas the relatively stronger H‐bonds in the T‐form are assisted by contribution from shared‐shell (covalent) interaction. The nonoccurrence of the double‐proton transfer reaction in the S0 state is argued from the large barrier for the transformation N‐form → T‐form (N‐form constitutes the global minimum on the S0‐PEC), whereas the stability order is reversed together with a marked reduction of the energy barrier in the S1‐PEC accounting for the ESDPT process.

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Theoretical insights into solvent‐polarity‐associated excited state behaviors for a novel 2‐hydroxy‐1‐naphthaldehyde‐triphenylamine (TPHY) fluorophore: A TDDFT study

Hou,

Zhang,

Zhao

et al. 2024

J Chinese Chemical Soc

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Inspired by the profound allure of the exquisitely regulated characteristics exhibited by 2‐hydroxy‐1‐naphthaldehyde‐triphenylamine (TPHY) and its derivatives in the realms of photochemistry and photophysics, our current endeavor primarily revolves around delving into the intricacies of photo‐induced excited state reactions for TPHY fluorophores within solvents boasting varying degrees of polarity. Our simulations, resulting from variations in geometry and vertical excitation charge reorganization, unveil solvent polarity‐dependent hydrogen bonding interactions and charge recombination induced by photoexcitation that can significantly enhance the excited state intramolecular proton transfer (ESIPT) reaction for TPHY chemosensor. By constructing potential energy surfaces (PESs), we reveal that the single ESIPT reaction of TPHY occurs concurrently with alternative dual intramolecular hydrogen bonds (O1‐H2···N3 and O4‐H5···N6). We sincerely hope that the regulation of solvent polarity on excited state behaviors may pave the way for the development of innovative luminescent materials.

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Regulated stepwise ESDPT mechanism associated with chalcogen substitutions in BDIBD derivatives

Abstract: Inspired by the brilliant photochemical and photophysical properties of organic molecule containing the chalcogenide substitutions that could be potentially applied across various disciplines, in this work, the effects of atomic...

Cited by 24 publications

References 65 publications

Theoretical Insights into the Effect of Different Numbers of Thiophene Groups on Hydrogen Bond Interaction and Excited-State Intramolecular Proton-Transfer Process for Flavonoid Derivatives

Theoretical Insights into the Effect of Different Numbers of Thiophene Groups on Hydrogen Bond Interaction and Excited-State Intramolecular Proton-Transfer Process for Flavonoid Derivatives

Deciphering the Differential Origin of Hydrogen Bonds in the Normal and Tautomer Forms of 7‐Azaindole:Piperidin‐2‐one Hydrogen‐Bonded Complex: Excited‐State Double Proton Transfer

Theoretical insights into solvent‐polarity‐associated excited state behaviors for a novel 2‐hydroxy‐1‐naphthaldehyde‐triphenylamine (TPHY) fluorophore: A TDDFT study

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