4.8 Article

On-off-on Control of Molecular Inversion Symmetry via Multi-stage Protonation: Elucidating Vibronic Laporte Rule

期刊

出版社

WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202212581

关键词

Laporte Rule; Molecular Symmetry; Nonlinear Optics; Protonation; Two-Photon Absorption

资金

  1. Ministry of Education and Research, Republic of Estonia [PRG690, PSG317, PRG661]
  2. European Regional Development Fund [TK134, TK141]
  3. National Science Center, Poland [HARMONIA 2018/30/M/ST5/00460]
  4. NSF [2103628]
  5. Division Of Chemistry
  6. Direct For Mathematical & Physical Scien [2103628] Funding Source: National Science Foundation

向作者/读者索取更多资源

The Laporte rule states that one- and two-photon absorption spectra of symmetric molecules should display alternatively forbidden electronic transitions. However, for organic fluorophores, the distinction between symmetric and non-inversion symmetric two-photon spectra is often unclear due to vibronic interactions. In this study, we use protonation to break and then reconstitute inversion symmetry in a symmetric diketopyrrolopyrrole, resulting in significant changes in two-photon absorption. Through experiments and calculations, we explain how low-frequency vibrational modes can lead to deviations from the Laporte rule and propose the system as an inversion symmetry switch for two-photon sensing applications.
The Laporte rule dictates that one- and two-photon absorption spectra of inversion-symmetric molecules should display alternatively forbidden electronic transitions; however, for organic fluorophores, drawing clear distinction between the symmetric- and non-inversion symmetric two-photon spectra is often obscured due to prevalent vibronic interactions. We take advantage of consecutive single- and double-protonation to break and then reconstitute inversion symmetry in a nominally symmetric diketopyrrolopyrrole, causing large changes in two-photon absorption. By performing detailed one- and two-photon titration experiments, with supporting quantum-chemical model calculations, we explain how certain low-frequency vibrational modes may lead to apparent deviations from the strict Laporte rule. As a result, the system may be indeed considered as an on-off-on inversion symmetry switch, opening new avenues for two-photon sensing applications.

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