Fluorescence Photoswitching of a Diarylethene by Irradiation with Single-Wavelength Visible Light

Article abstract of DOI:10.1021/jacs.7b10697

Photoswitchable turn-on mode fluorescent molecules have been so far successfully used in super-resolution fluorescence microscopies. Here, we report on fluorescence photoswitching of 1,2-bis(2-ethyl-6-phenyl-1-benzothiophene-1,1-dioxide-3-yl)perfluorocyclopentene (1) by irradiation with single-wavelength visible (420 nm < λ < 470 nm) light, the wavelength of which is longer than the 0-0 transition of open-ring isomer 1a, without UV light excitation. By absorbing very weak hot bands or Urbach tails 1a underwent a cyclization reaction to produce fluorescent closed-ring isomer 1b. Both cyclization and cycloreversion reactions of 1 took place with the visible light in the far off-resonance region of the absorption edge. Based on numerical simulations of the formation process of 1b from 1a by irradiation with 450 nm light, weak absorption coefficients at 450 nm in n-hexane and CCl₄ were estimated to be 0.084 and 0.19 M^-1 cm^-1, respectively. The reversible fluorescence photoswitching with the single visible light is advantageously applicable to super-resolution fluorescence imaging in biological systems.

Full text of DOI:10.1021/jacs.7b10697

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Communication
Fluorescence Photoswitching of a Diarylethene by
Irradiation with Single-Wavelength Visible Light
Ryota Kashihara, Masakazu Morimoto, Syoji Ito, Hiroshi Miyasaka, and Masahiro Irie
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.7b10697 • Publication Date (Web): 07 Nov 2017
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Fluorescence Photoswitching of a Diarylethene by Irradiation
with Single-Wavelength Visible Light
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Ryota Kashihara,† Masakazu Morimoto,† Syoji Ito,‡ Hiroshi Miyasaka,‡ Masahiro Irie*,†
†Department of Chemistry and Research Center for Smart Molecules, Rikkyo University, NishiꢀIkebukuro 3ꢀ34ꢀ1, Toshimaꢀ
ku, Tokyo, 171ꢀ8501, Japan
‡Division of Frontier Materials Science and Center for Advanced Interdisciplinary Research, Graduate School of Engineerꢀ
ing Science, Osaka University, Toyonaka, Osaka 560ꢀ8531, Japan
Supporting Information Placeholder
1,2ꢀbis(2ꢀmethylꢀ1ꢀbenzothiophenꢀ3ꢀyl)perfluorocyclopentene.
When the methyl groups at 2ꢀ and 2′ꢀpoistions are replaced with
short alkyl chains, and aryl groups are substituted at 6ꢀ and 6′ꢀ
positions, the diarylethene derivatives were found to increase the
fluorescence quantum yield of the closedꢀring isomers up to ~ 0.9
and the absorption coefficient up to ~ 6 × 104 M−1 cm−1.19 The
derivatives have been successfully applied to superꢀresolution
fluorescence microscopies, such as PALM and STORM20ꢀ22 and
RESOLFT (reversible saturable (switchable) optical linear fluoꢀ
rescence transitions) microscopy.23
ABSTRACT: Photoswitchable turnꢀon mode fluorescent moleꢀ
cules have been so far successfully used in superꢀresolution fluoꢀ
rescence microscopies. Here, we report on fluorescence phoꢀ
toswitching of 1,2ꢀbis(2ꢀethylꢀ6ꢀphenylꢀ1ꢀbenzothiopheneꢀ1,1ꢀ
dioxideꢀ3ꢀyl)perfluorocyclopentene (1) by irradiation with singleꢀ
wavelength visible (420 nm < λ < 470 nm) light, the wavelength
of which is longer than the 0ꢀ0 transition of openꢀring isomer 1a,
without UV light excitation. By absorbing very weak hot bands or
Urbach tails 1a underwent a cyclization reaction to produce fluoꢀ
rescent closedꢀring isomer 1b. Both cyclization and cycloreverꢀ
sion reactions of 1 took place with the visible light in the far offꢀ
resonance region of the absorption edge. Based on numerical
simulations of the formation process of 1b from 1a by irradiation
with 450 nm light, weak absorption coefficients at 450 nm in nꢀ
hexane and CCl4 were estimated to be 0.084 and 0.19 M−1 cm−1,
respectively. The reversible fluorescence photoswitching with the
single visible light is advantageously applicable to superꢀ
resolution fluorescence imaging in biological systems.
During the course of study on the above photoswitchable diꢀ
arylethenes we have discovered unprecedented photoreactions of
1,2ꢀbis(2ꢀethylꢀ6ꢀphenylꢀ1ꢀbenzothiopehneꢀ1,1ꢀdioxideꢀ3ꢀ
yl)perfluorocyclopentene (1). Upon irradiation with singleꢀ
wavelength visible light 1 underwent reversible photoisomerizaꢀ
tion reactions and showed fluorescence photoswitching.
Recently, considerable efforts have been paid to develop moꢀ
lecular photoswitches, which are capable to modulate physical
and chemical properties of materials as well as biological activiꢀ
ties upon photoirradiation.1ꢀ9 Among them photoswitchable fluoꢀ
rescent molecules attract special interests because of their possible
applications to ultrahigh density optical memory media10ꢀ12 and
superꢀresolution fluorescence microscopies.12ꢀ16 The reversibly
photoswitchable fluorescent molecules have been constructed by
combining both photochromic and fluorescent chromophores in a
molecule.10,11 These molecules are initially fluorescent, while the
fluorescence is quenched by an energy or an electron transfer
mechanism when the photochromic unit undergoes the phoꢀ
toisomerization reaction. The turnꢀoff mode fluorescence switchꢀ
ing can be applied to optical memory media, but is hardly appliꢀ
cable to superꢀresolution fluorescence imaging, such as PALM
(photoactivated localization microscopy) and STORM (stochastic
optical reconstruction microscopy), because the imaging techꢀ
niques require a dark back ground to detect single fluorescent
molecules.17 Turnꢀon mode fluorescent molecules are favorable
for the superꢀresolution microscopies. A new type of phoꢀ
toswitchable fluorescent molecules, which have no fluorophore
unit but exhibit turnꢀon mode fluorescence upon photoirradiation,
have recently been developed.18 They are sulfone derivatives of
Figure 1 shows an absorption spectrum of 1a and absorption
and fluorescence spectra of 1b in 1,4ꢀdioxane. Upon irradiation
with UV (365 nm) light, 1a readily converted to 1b, which exhibꢀ
its fluorescence. The photobleaching process of 1b is also shown
in Fig. 1. 1b reverted back to initial 1a upon irradiation with 450
nm light. The cycloreversion reaction was followed by measuring
the fluorescence of 1b, because the fluorescence intensity is proꢀ
portional to the amount of 1b and a small amount of 1b can be
detected by the fluorescence. Although the fluorescence considerꢀ
ably decreased, noticeable intensity of fluorescence ascribed 1b
remained even after prolonged irradiation with 450 nm light. The
absorption band of 1a locates shorter than 400 nm and the 0ꢀ0
transition is around 400 nm. Therefore, 1a has no apparent abꢀ
sorption at 450 nm. This means that all closedꢀring 1b isomers are
expected to completely revert back to openꢀring 1a isomers by
irradiation with 450 nm light. But, a small amount of 1b survived.
This result indicates that 450 nm light induces the cyclization
reaction of 1a in addition to the cycloreversion reaction, though
there is no apparent absorption of 1a at the wavelength.
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Figure 2. Fluorescence intensity of 1 in the photostationary state
in nꢀhexane (black) and CCl4 (red) under irradiation with monoꢀ
chromatic 500, 488, 480, 471, 468, 465, 460, 450, and 440 nm
light. The excitation wavelength for the fluorescence was 450 nm.
Another possible mechanism is that the photoreaction is inꢀ
duced by absorbing very weak hot bands24 or Urbach tails.25ꢀ28 To
verify the hot band mechanism the photoreactions induced upon
irradiation with 450 nm was examined in detail. The reversible
photocyclization/photocycloreversion reactions between openꢀ
ring isomer 1a and closedꢀring isomer 1b are expressed as folꢀ
lows. We assumed that the reversible photoisomerizations are
induced by irradiation with singleꢀwavelength (λ) light.
Figure 1. (a) Absorption and fluorescence spectral changes of 1 in
1,4ꢀdioxane (3.2 × 10−6 M) upon irradiation with UV light (365
nm) and subsequent monochromatic 450 nm light. The solid black
line showed the absorption spectrum of 1a. Dashed lines showed
the absorption spectra of 1b. (b) Fluorescence spectral changes of
1b in 1,4ꢀdioxane upon prolonged irradiation with monochromatic
450 nm light. The fluorescence intensity after irradiation with 450
nm for 150 min was the same as the intensity after irradiation for
140 min.
Openꢀring isomer 1a
Closedꢀring isomer 1b
(1)
(2)
ꢀꢁB
ꢄ
ꢇ
ꢈ
ꢃ ΦABεAꢅA ꢆ ΦBAεBꢅB
ꢀꢂ
ꢄ
ꢇ
ꢋ
1 ꢆ 10ꢉ ε ꢁ ꢊε ꢁ
10ꢎꢏꢐ
ꢑ
A
A
B B
In order to elucidate the unprecedented result we investigated
following two mechanisms. One of possible mechanisms is that
antiꢀStokes Raman scattering lines induce the photoreactions. The
Stokes Raman scattering of nꢀhexane has strong lines at around
2900 cm−1, while the Raman scattering of carbon tetrachloride
(CCl4) has no notable lines longer than 790 cm−1 (see Fig. S1). In
these two solvents we measured the threshold wavelength of light,
which can induce the photocyclization reaction of 1a. According
to this antiꢀStokes Raman scattering mechanism, the reaction
threshold wavelength in nꢀhexane is expected to be longer than
the wavelength in CCl4. Figure 2 shows the fluorescence increase
in the photostationary state under irradiation with monochromatic
500, 488, 480, 471, 468, 465, 460, 450, and 440 nm light (see Fig.
S2). The fluorescence intensity correlates to the amount of the
photogenerated 1b, because the fluorescence quantum yields of
1b in CCl4 and nꢀhexane are almost similar, as shown in Table 1.
The threshold wavelength in CCl4 was observed at 471 nm, while
the wavelength in nꢀhexane shifted to 460 nm. The shorter waveꢀ
length shift of the reaction threshold in nꢀhexane contradicts the
antiꢀStokes Raman scattering mechanism. The absence of oxygen
effect also excludes the contribution of triplet states in CCl4.
ꢈ ꢃ
ꢍ
εAꢅA ꢌ εBꢅB
, where ΦAB, ΦBA, εA, εB, CA, CB, d, and I0 are the cyclization
quantum yield, the cycloreversion quantum yield, the absorption
coefficient of 1a at λ, the absorption coefficient of 1b at λ, the
concentration of 1a (M), the concentration of 1b (M), the cell
length (cm), and the light intensity (einstein/cm2·s), respectively.
When εACA + εBCB << 1, the formation of the closedꢀring isomers
upon irradiation with singleꢀwavelength (λ) light is expressed as
follows, where Co is the total concentration of 1a and 1b.
ꢖ
ΦABεA
ꢄ
ꢇ
ABεAꢊΦBAεB
ꢘ
ꢅꢒ ꢃ
ꢅoꢓ1 ꢆ ꢔꢉ Φ
ꢍꢕꢐ ꢗ ꢂꢙ
(3)
(4)
ΦABεAꢊΦBAεB
In the photostationary state,
ꢁꢚ
ΦABεA
ꢃ Φ
ꢁꢛ
ABεAꢊΦBAεB
Table 1. Photochemical and photophysical properties of 1.
Solvent
ΦF
nꢀHexane
0.92
CCl4
0.89
1,4ꢀDioxane
0.87
0.62
ΦAB
0.42
0.50
ΦBA
1.3 × 10−3
6.6 × 10−4
5.9 × 10−4
εA (450 nm) / M−1 cm−1
εB (450 nm) / M−1 cm−1
Conversion (CB / C0) a
0.084
0.19
0.39
4.5 × 104
6.0 × 10−4
4.3 × 104
3.4 × 10−3
4.5 × 104
9.1 × 10−3
a The ratio of photogenerated closedꢀring isomer 1b in the photostationary state under irradiation with 450 nm light.
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Figure 3 shows the formation of 1b from pure 1a in nꢀhexane
According to Wondrazek et al.26 and Kinoshita et al.27 the abꢀ
sorption spectra (or the emission excitation spectra) of fluorescent
dyes, such as coumarin 7 and rhodamine 6G, show an exponential
frequency dependence in the far offꢀresonance region of the abꢀ
sorption tails at room temperature. The tails have been reported to
obey the Urbach rule known in the absorption spectra of solid
materials, as expressed by the following formula.25ꢀ28
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3
4
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6
7
8
and in CCl4 upon irradiation with 450 nm light. To detect a very
small amount of 1b, less than 10−7 M, fluorescence was used to
measure the concentrations of 1b (see SI). The formation curves
were analyzed according to eq. (3). The curves are well reproꢀ
duced by using the equation. Based on the analysis the conversion
ratios in the photostationary state in nꢀhexane and CCl4 under
irradiation with 450 nm light were determined to be 0.060% and
0.34%, respectively. It is possible to estimate the weak absorption
coefficients of 1a, εA, at 450 nm from the photostationary converꢀ
sion ratios. The cyclization and cycloreversion quantum yields,
ΦAB and ΦBA, and absorption coefficients of 1b, εB, were measꢀ
ured by independent experiments.19c,d Table 1 shows the weak
absorption coefficients at 450 nm estimated from eq. (4) along
with the quantum yields of cyclization and cycloreversion reacꢀ
tions, and the fluorescence quantum yields in nꢀhexane and CCl4.
The absorption coefficient at 450 nm in 1,4ꢀdioxane can also be
estimated from Fig. 1. The fluorescence intensity obtained after
irradiating 1b with 450 nm light for 150 min, as shown in Fig. 1b,
agreed to the intensity generated by irradiating 1a with 450 nm
light for 60 min. The coefficient in 1,4ꢀdioxane, 0.39 M−1 cm−1,
was larger than the values in nꢀhexane (0.084 M−1 cm−1) and CCl4
(0.19 M−1 cm−1). Although the absorption coefficients were very
low, the formation of 1b was clearly observed upon irradiation
with 450 nm light. This is attributed to very low cycloreversion
quantum yields of 1b, ΦBA: less than ~ 10−3, in these solvents.
ꢄ
ꢇ
ꢞ ꢟꢘꢘꢉꢟ
ꢄ ꢇ
ꢄ
ꢇ
ε ꢜ ∝ ε ꢜꢐꢐ exp ꢝꢆ
ꢢ
(5)
ꢠBꢡ
, where ε, kB, T, and σ are the absorption coefficient, the Boltzꢀ
mann constant, the absolute temperature of the sample and the
steepness parameter, respectively. As described above, very weak
absorption coefficients at the wavelengths, where apparent abꢀ
sorption is absent, can be estimated from eq. (4) by measuring the
conversion ratios in the photostationary state. The conversion
ratios were measured by irradiation with monochromatic 440 nm,
435 nm and 429 nm light in addition to 450 nm light in nꢀhexane
and CCl4. The absorption coefficients estimated from eq. (4) were
plotted in Fig. 4 along with the absorption tails of the openꢀring
isomer 1a. As can be seen from Fig. 4 the coefficients obey the
exponential frequency dependence at the wavelengths longer than
~ 415 nm (~ 24000 cm−1). The σ values in nꢀhexane and CCl4
were obtained to be around 0.7, which is slightly lower than the
values observed for coumarin 7 and rhodamine 6G.
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The exponential frequency dependence shown in Fig. 4 indiꢀ
cates that the unprecedented photoreactions induced with the visiꢀ
ble light in the far offꢀresonance region of the absorption edge are
caused by the absorption of hot bands or Urbach tails. The openꢀ
ring 1a isomers in the vibrationally excited states undergo optical
transition into electronically excited states by absorbing the very
weak hot bands and the cyclization reaction from 1a to 1b takes
place. At the same time, the visible light induces the cycloreverꢀ
sion reaction from 1b to 1a. After prolonged irradiation, the sysꢀ
tem reaches the photostationary state. Both cyclization and cyꢀ
cloreversion reactions can be induced by irradiation with singleꢀ
wavelength visible (420 < λ < 470 nm) light. Although the absorpꢀ
tion coefficients of 1a at the visibleꢀwavelength region are very
small, the very low cycloreversion quantum yields of 1b, less than
~ 10−3, result in the presence of 1b in the photostationary state.29
Eq. (4) also indicates that the light intensity does not influence
the conversion ratios in the photostationary state. Figure 3 also
shows the formation of 1b upon irradiation with low (1/4) intensiꢀ
ty light. Even when the irradiation intensity was decreased to 1/4,
the conversion ratios in the photostationary state were the same as
those of full intensity light.
Figure 3. Formations of closedꢀring isomer 1b from pure 1a (1.0
× 10−5 M) in nꢀhexane (a) and CCl4 (b) upon irradiation with
monochromatic 450 nm light. The two formation curves were
measured by changing the light intensity, 100% (blue) and 25%
(red), respectively. Solid lines were simulated by using eq (3).
Figure 4. Logarithmic plot of molar absorption coefficients of 1a
(εA) in nꢀhexane (red) and CCl4 (blue) obtained from absorption
spectra of 1a (closed circles) and fluorescence intensities of 1b in
the photostationary states under irradiation with monochromatic
visible light (open circles).
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In conclusion, reversible fluorescence photoswitching of 1 was
induced by irradiation with singleꢀwavelength visible light, the
wavelength of which is longer than the 0ꢀ0 transition of 1a. The
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the singleꢀwavelength visible light sensitivity can be advantaꢀ
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such as PALM and STORM.
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ASSOCIATED CONTENT
Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: ######/##########.
Experimental details and additional data (PDF)
AUTHOR INFORMATION
Corresponding Author
*iriem@rikkyo.ac.jp
Notes
The authors declare no competing financial interests.
ACKNOWLEDGMENT
This work was supported by JSPS KAKENHI Grant Numbers
JP26107002,
JP26288009,
JP15H01096,
JP15K13625,
JP16H03827, JP16H06505, JP17H05272 and MEXTꢀSupported
Program for the Strategic Research Foundation at Private Univerꢀ
sities. The authors wish to thank Prof. Satoshi Kawata at Osaka
University for his helpful discussion on Raman scattering.
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