Unraveling the dispersed kinetics of dichlorofluorescein in potassium hydrogen phthalate crystals

Eric D. Bott, Erin A. Riley, Bart Kahr, Philip J. Reid

Research output: Contribution to journalArticle

Abstract

The connection between photoluminescence (PL) intermittency and excited-state kinetics is explored for 2′,7′-dichlorofluorecin (DCF) isolated in crystals of potassium acid phthalate (KAP) using time-tagged, time-resolved, time-correlated single-photon counting (T3R-TCSPC). In this technique, PL intermittency or "blinking" is measured in conjunction with the time of photon arrival relative to photoexcitation, allowing for the correlation of emissive intensities and excited-state decay kinetics of single molecules. The blinking trace is parsed into emissive and nonemissive segments using change-point-detection analysis, and the duration of these segments are used to quantify PL intermittency. The results presented here demonstrate that two populations of DCF exist in KAP, with one population demonstrating single-exponential excited state decay over the course of the blinking trace, and the other demonstrating stretched-exponential decay. Molecules demonstrating single-exponential decay also demonstrate modest intensity variation in the blinking trace. Correlation of the emission intensity and excited-state lifetimes demonstrates that for these molecules spectral diffusion is largely responsible for the evolution in emission intensity. In contrast, molecules demonstrating nonexponential excited-state decay vary in emission intensity. Correlation of the emissive intensities with the excited-state lifetimes demonstrates that these molecules undergo changes in both radiative and nonradiative decay rate constants as well as spectral diffusion. These observations suggest that DCF exists in two environments in KAP differentiated by the propensity for proton-transfer with the surrounding KAP matrix. The results presented here provide further insight into the origin of PL intermittency demonstrated by DCF in KAP and related systems.

Original languageEnglish (US)
Pages (from-to)7331-7337
Number of pages7
JournalJournal of Physical Chemistry A
Volume114
Issue number27
DOIs
StatePublished - Jul 15 2010

Fingerprint

Blinking
phthalates
Excited states
blinking
potassium
intermittency
Crystals
Kinetics
Photoluminescence
kinetics
hydrogen
Molecules
Photons
excitation
crystals
decay
photoluminescence
molecules
Population
Protons

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Medicine(all)

Cite this

Unraveling the dispersed kinetics of dichlorofluorescein in potassium hydrogen phthalate crystals. / Bott, Eric D.; Riley, Erin A.; Kahr, Bart; Reid, Philip J.

In: Journal of Physical Chemistry A, Vol. 114, No. 27, 15.07.2010, p. 7331-7337.

Research output: Contribution to journalArticle

Bott, Eric D. ; Riley, Erin A. ; Kahr, Bart ; Reid, Philip J. / Unraveling the dispersed kinetics of dichlorofluorescein in potassium hydrogen phthalate crystals. In: Journal of Physical Chemistry A. 2010 ; Vol. 114, No. 27. pp. 7331-7337.
@article{b029d6a9d5a44ae3838ca2e5865344e5,
title = "Unraveling the dispersed kinetics of dichlorofluorescein in potassium hydrogen phthalate crystals",
abstract = "The connection between photoluminescence (PL) intermittency and excited-state kinetics is explored for 2′,7′-dichlorofluorecin (DCF) isolated in crystals of potassium acid phthalate (KAP) using time-tagged, time-resolved, time-correlated single-photon counting (T3R-TCSPC). In this technique, PL intermittency or {"}blinking{"} is measured in conjunction with the time of photon arrival relative to photoexcitation, allowing for the correlation of emissive intensities and excited-state decay kinetics of single molecules. The blinking trace is parsed into emissive and nonemissive segments using change-point-detection analysis, and the duration of these segments are used to quantify PL intermittency. The results presented here demonstrate that two populations of DCF exist in KAP, with one population demonstrating single-exponential excited state decay over the course of the blinking trace, and the other demonstrating stretched-exponential decay. Molecules demonstrating single-exponential decay also demonstrate modest intensity variation in the blinking trace. Correlation of the emission intensity and excited-state lifetimes demonstrates that for these molecules spectral diffusion is largely responsible for the evolution in emission intensity. In contrast, molecules demonstrating nonexponential excited-state decay vary in emission intensity. Correlation of the emissive intensities with the excited-state lifetimes demonstrates that these molecules undergo changes in both radiative and nonradiative decay rate constants as well as spectral diffusion. These observations suggest that DCF exists in two environments in KAP differentiated by the propensity for proton-transfer with the surrounding KAP matrix. The results presented here provide further insight into the origin of PL intermittency demonstrated by DCF in KAP and related systems.",
author = "Bott, {Eric D.} and Riley, {Erin A.} and Bart Kahr and Reid, {Philip J.}",
year = "2010",
month = "7",
day = "15",
doi = "10.1021/jp102194u",
language = "English (US)",
volume = "114",
pages = "7331--7337",
journal = "Journal of Physical Chemistry A",
issn = "1089-5639",
publisher = "American Chemical Society",
number = "27",

}

TY - JOUR

T1 - Unraveling the dispersed kinetics of dichlorofluorescein in potassium hydrogen phthalate crystals

AU - Bott, Eric D.

AU - Riley, Erin A.

AU - Kahr, Bart

AU - Reid, Philip J.

PY - 2010/7/15

Y1 - 2010/7/15

N2 - The connection between photoluminescence (PL) intermittency and excited-state kinetics is explored for 2′,7′-dichlorofluorecin (DCF) isolated in crystals of potassium acid phthalate (KAP) using time-tagged, time-resolved, time-correlated single-photon counting (T3R-TCSPC). In this technique, PL intermittency or "blinking" is measured in conjunction with the time of photon arrival relative to photoexcitation, allowing for the correlation of emissive intensities and excited-state decay kinetics of single molecules. The blinking trace is parsed into emissive and nonemissive segments using change-point-detection analysis, and the duration of these segments are used to quantify PL intermittency. The results presented here demonstrate that two populations of DCF exist in KAP, with one population demonstrating single-exponential excited state decay over the course of the blinking trace, and the other demonstrating stretched-exponential decay. Molecules demonstrating single-exponential decay also demonstrate modest intensity variation in the blinking trace. Correlation of the emission intensity and excited-state lifetimes demonstrates that for these molecules spectral diffusion is largely responsible for the evolution in emission intensity. In contrast, molecules demonstrating nonexponential excited-state decay vary in emission intensity. Correlation of the emissive intensities with the excited-state lifetimes demonstrates that these molecules undergo changes in both radiative and nonradiative decay rate constants as well as spectral diffusion. These observations suggest that DCF exists in two environments in KAP differentiated by the propensity for proton-transfer with the surrounding KAP matrix. The results presented here provide further insight into the origin of PL intermittency demonstrated by DCF in KAP and related systems.

AB - The connection between photoluminescence (PL) intermittency and excited-state kinetics is explored for 2′,7′-dichlorofluorecin (DCF) isolated in crystals of potassium acid phthalate (KAP) using time-tagged, time-resolved, time-correlated single-photon counting (T3R-TCSPC). In this technique, PL intermittency or "blinking" is measured in conjunction with the time of photon arrival relative to photoexcitation, allowing for the correlation of emissive intensities and excited-state decay kinetics of single molecules. The blinking trace is parsed into emissive and nonemissive segments using change-point-detection analysis, and the duration of these segments are used to quantify PL intermittency. The results presented here demonstrate that two populations of DCF exist in KAP, with one population demonstrating single-exponential excited state decay over the course of the blinking trace, and the other demonstrating stretched-exponential decay. Molecules demonstrating single-exponential decay also demonstrate modest intensity variation in the blinking trace. Correlation of the emission intensity and excited-state lifetimes demonstrates that for these molecules spectral diffusion is largely responsible for the evolution in emission intensity. In contrast, molecules demonstrating nonexponential excited-state decay vary in emission intensity. Correlation of the emissive intensities with the excited-state lifetimes demonstrates that these molecules undergo changes in both radiative and nonradiative decay rate constants as well as spectral diffusion. These observations suggest that DCF exists in two environments in KAP differentiated by the propensity for proton-transfer with the surrounding KAP matrix. The results presented here provide further insight into the origin of PL intermittency demonstrated by DCF in KAP and related systems.

UR - http://www.scopus.com/inward/record.url?scp=77954443798&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=77954443798&partnerID=8YFLogxK

U2 - 10.1021/jp102194u

DO - 10.1021/jp102194u

M3 - Article

VL - 114

SP - 7331

EP - 7337

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

SN - 1089-5639

IS - 27

ER -