Steady-State Spectroscopy to Single Out the Contact
Ion Pair in Excited-State Proton Transfer
Version 2 2021-03-01, 18:40
Version 1 2021-02-09, 17:44
Posted on 2021-03-01 - 18:40
Despite the outstanding
relevance of proton transfer reactions,
investigations of the solvent dependence on the elementary step are
scarce. We present here a probe system of a pyrene-based photoacid
and a phosphine oxide, which forms stable hydrogen-bonded complexes
in aprotic solvents of a broad polarity range. By using a photoacid,
an excited-state proton transfer (ESPT) along the hydrogen bond can
be triggered by a photon and observed via fluorescence spectroscopy.
Two emission bands could be identified and assigned to the complexed
photoacid (CPX) and the hydrogen-bonded ion pair (HBIP) by a solvatochromism
analysis based on the Lippert–Mataga model. The latter indicates
that the difference in the change of the permanent dipole moment of
the two species upon excitation is ∼3 D. This implies a displacement
of the acidic hydrogen by ∼65 pm, which is in quantitative
agreement with a change of the hydrogen bond configuration from O–H···O
to –O···H–O+.
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Grandjean, Alexander; Pérez Lustres, J. Luis; Muth, Stephan; Maus, Daniel; Jung, Gregor (2021). Steady-State Spectroscopy to Single Out the Contact
Ion Pair in Excited-State Proton Transfer. ACS Publications. Collection. https://doi.org/10.1021/acs.jpclett.0c03593
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AUTHORS (5)
AG
Alexander Grandjean
JP
J. Luis Pérez Lustres
SM
Stephan Muth
DM
Daniel Maus
GJ
Gregor Jung
KEYWORDS
CPXESPTpyrene-based photoacidpolarity rangeemission bandssolvatochromism analysisprobe systemhydrogen-bonded ion pairproton transfer reactionsacidic hydrogenfluorescence spectroscopycomplexed photoacidHBIPexcited-state proton transferExcited-State Proton TransferContact Ion PairSteady-State Spectroscopyphosphine oxideaprotic solventshydrogen bondhydrogen-bonded complexeshydrogen bond configuration