On-off-on Control of Molecular Inversion Symmetry via Multi-stage Protonation: Elucidating Vibronic Laporte Rule
Oglądaj/ Otwórz
Data
2022Autor
Stark, Charles W.
Rammo, Matt
Trummal, Aleksander
Uudsemaa, Merle
Pahapill, Juri
Sildoja, Meelis-Mait
Tshepelevitsh, Sofja
Leito, Ivo
Young, David C.
Szymański, Bartosz
Vakuliuk, Olena
Gryko, Daniel T.
Rebane, Aleksander
Metadane
Pokaż pełny rekordStreszczenie
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.
Kolekcje
- Artykuły IChO PAN [112]
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