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Investigating Design Rules for Photoinduced Electron Transfer Quenching in Triangulenium Probes

Dahl Jensen, Jesper ; Jakobsen, Rasmus K. ; Yao, Zehan LU and Laursen, Bo W. (2023) In Chemistry - A European Journal 29(46).
Abstract

Fluorescent probes based on photoinduced electron transfer (PET) quenching of long lifetime triangulenium fluorophores have found multiple applications. For such probes a successful design relies on the right balance between the rate of PET quenching and fluorescence. In a series of ADOTA (A) and DAOTA (D) triangulenium fluorophores appended with aniline-like quencher moieties, we have investigated the rate of quenching and its relation to thermodynamic driving force, distance, and conjugation within the quencher moiety. Three different quenchers, a short (1), a long (2), and a long twisted (3), 4-aminophenyl, 4’-aminobiphenyl, and 2,2’-dimethyl-4’-aminobiphenyl, respectively were investigated. Steady-state spectroscopy and... (More)

Fluorescent probes based on photoinduced electron transfer (PET) quenching of long lifetime triangulenium fluorophores have found multiple applications. For such probes a successful design relies on the right balance between the rate of PET quenching and fluorescence. In a series of ADOTA (A) and DAOTA (D) triangulenium fluorophores appended with aniline-like quencher moieties, we have investigated the rate of quenching and its relation to thermodynamic driving force, distance, and conjugation within the quencher moiety. Three different quenchers, a short (1), a long (2), and a long twisted (3), 4-aminophenyl, 4’-aminobiphenyl, and 2,2’-dimethyl-4’-aminobiphenyl, respectively were investigated. Steady-state spectroscopy and electrochemistry confirms that the quencher moieties are electronically decoupled from the dyes and have similar oxidation potentials and thus driving force for PET quenching, irrespectively of their different length and conjugation. Time-resolved fluorescence measurement was used to measure the fast PET quenching, with rate constant kPET ranging from >4×1011 to 2×109 s−1. Interestingly, PET quenching is equally efficient/fast from 1 and 2, even with increase in distance between the donor and the acceptor. However, when twisting the biphenyl in 3, a 20-fold decrease in quenching is found. Even with this decrease in kPET, the quenching in 3 A/D is still highly efficient, with nearly 99 % quenching. The study show that long lifetime fluorophores can be efficiently switched even by relatively slow PET processes and that PET quencher moieties can be removed far from the fluorophore if conjugated linkers are applied.

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author
; ; and
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
fluorescence spectroscopy, organic chromophores, PET quenching, pH probes, ps spectroscopy, triangulenium dyes
in
Chemistry - A European Journal
volume
29
issue
46
article number
e202301077
publisher
Wiley-Blackwell
external identifiers
  • pmid:37261711
  • scopus:85165269941
ISSN
0947-6539
DOI
10.1002/chem.202301077
language
English
LU publication?
yes
id
3ef960ce-d7e0-4434-a074-e176881b5138
date added to LUP
2023-10-03 11:28:58
date last changed
2024-04-19 01:51:11
@article{3ef960ce-d7e0-4434-a074-e176881b5138,
  abstract     = {{<p>Fluorescent probes based on photoinduced electron transfer (PET) quenching of long lifetime triangulenium fluorophores have found multiple applications. For such probes a successful design relies on the right balance between the rate of PET quenching and fluorescence. In a series of ADOTA (A) and DAOTA (D) triangulenium fluorophores appended with aniline-like quencher moieties, we have investigated the rate of quenching and its relation to thermodynamic driving force, distance, and conjugation within the quencher moiety. Three different quenchers, a short (1), a long (2), and a long twisted (3), 4-aminophenyl, 4’-aminobiphenyl, and 2,2’-dimethyl-4’-aminobiphenyl, respectively were investigated. Steady-state spectroscopy and electrochemistry confirms that the quencher moieties are electronically decoupled from the dyes and have similar oxidation potentials and thus driving force for PET quenching, irrespectively of their different length and conjugation. Time-resolved fluorescence measurement was used to measure the fast PET quenching, with rate constant k<sub>PET</sub> ranging from &gt;4×10<sup>11</sup> to 2×10<sup>9</sup> s<sup>−1</sup>. Interestingly, PET quenching is equally efficient/fast from 1 and 2, even with increase in distance between the donor and the acceptor. However, when twisting the biphenyl in 3, a 20-fold decrease in quenching is found. Even with this decrease in k<sub>PET,</sub> the quenching in 3 A/D is still highly efficient, with nearly 99 % quenching. The study show that long lifetime fluorophores can be efficiently switched even by relatively slow PET processes and that PET quencher moieties can be removed far from the fluorophore if conjugated linkers are applied.</p>}},
  author       = {{Dahl Jensen, Jesper and Jakobsen, Rasmus K. and Yao, Zehan and Laursen, Bo W.}},
  issn         = {{0947-6539}},
  keywords     = {{fluorescence spectroscopy; organic chromophores; PET quenching; pH probes; ps spectroscopy; triangulenium dyes}},
  language     = {{eng}},
  month        = {{08}},
  number       = {{46}},
  publisher    = {{Wiley-Blackwell}},
  series       = {{Chemistry - A European Journal}},
  title        = {{Investigating Design Rules for Photoinduced Electron Transfer Quenching in Triangulenium Probes}},
  url          = {{http://dx.doi.org/10.1002/chem.202301077}},
  doi          = {{10.1002/chem.202301077}},
  volume       = {{29}},
  year         = {{2023}},
}