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Electrocyclic reactions are reversible reactions. They involve an intramolecular cyclization or ring-opening of a conjugated polyene. Shown below are two examples of electrocyclic reactions. In the first reaction, the formation of the cyclic product is favored. In contrast, in the second reaction, ring-opening is favored due to the high ring strain associated with cyclobutene formation.
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The Cope rearrangement is classified as a [3,3] sigmatropic shift in 1,5-dienes, leading to a more stable, isomeric 1,5-diene. The reaction involves a concerted movement of six electrons, four from two π bonds and two from a σ bond, via an energetically favorable chair-like transition state.
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Sigmatropic rearrangements are a class of pericyclic reactions in which a σ bond migrates from one part of a π system to another. These are intramolecular rearrangements where the total number of σ and π bonds remain unchanged.
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Stepwise Excited-State Intramolecular Double Proton Transfer in 1,8-Dihydroxynaphthalene-2,7-dicarbaldehyde.

Diksha Pandey1, Sivaranjana Reddy Vennapusa1

  • 1School of Chemistry, Indian Institute of Science Education and Research Thiruvananthapuram, Maruthamala P. O., Vithura, Thiruvananthapuram 695551, Kerala, India.

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This study explores excited-state intramolecular double proton transfer in DHDA. Simulations show proton transfer occurs in the S1 state, leading to dual fluorescence emission.

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Area of Science:

  • Photochemistry
  • Theoretical Chemistry
  • Molecular Dynamics

Background:

  • Excited-state intramolecular double proton transfer (ESIDPT) is a crucial process in photochemistry.
  • Understanding ESIDPT mechanisms is key to designing novel photoresponsive materials.

Purpose of the Study:

  • To theoretically investigate the stepwise excited-state intramolecular double proton transfer (ESIDPT) in 1,8-dihydroxynaphthalene-2,7-dicarbaldehyde (DHDA).
  • To elucidate the dynamics and timescales of single and double proton transfer events.
  • To explore the relationship between tautomer stability and fluorescence emission.

Main Methods:

  • Utilized surface trajectory simulations.
  • Employed time-dependent density functional theory (TD-B3LYP) with the 6-31G(d) basis set.
  • Analyzed proton transfer pathways and timescales.

Main Results:

  • Proton transfer predominantly occurs in the S1 excited state.
  • Approximately 42% of trajectories exhibited single proton transfer (average time ~147 fs).
  • Double proton transfer was observed in ~32% of trajectories, with the first step averaging ~54 fs and the second step ~151 fs.
  • All three tautomers (normal, single, and double proton-transferred) show stable minima in the S1 state.
  • The S1 state exhibits ππ* character, leading to dual fluorescence emission.

Conclusions:

  • DHDA undergoes stepwise ESIDPT primarily through the S1 state.
  • The observed tautomer stability and ππ* character in the S1 state explain the dual fluorescence emission phenomenon.
  • This research provides insights into the photophysical behavior of DHDA and related molecules.