In situ preparation of highly fluorescent pyrene-dyes from non-luminous precursors upon photoirradiation

Article abstract of DOI:10.1039/c3cc40827b

The non-luminous precursor, 2-(1-pyrenyl)-9,10-dihydro-9,10- ethanoanthracene-11,12-dione, was photochemically converted to highly-fluorescent 2-(1-pyrenyl)anthracene quantitatively in solution and in the PMMA film and the fluorescence quantum yield of th

Full text of DOI:10.1039/c3cc40827b

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In Situ Preparation of Highly Fluorescent Pyrene-Dyes from Non-
luminous Precursors Upon Photoirradiation
Tatsuya Aotake,a Hiroshi Tanimoto,b Hidekatsu Hotta,b Daiki Kuzuhara,a Tetsuo Okujima,b Hidemitsu
Uno,b and Hiroko Yamada,*,a,c
5
Received (in XXX, XXX) Xth XXXXXXXXX 200X, Accepted Xth XXXXXXXXX 200X
First published on the web Xth XXXXXXXXX 200X
DOI: 10.1039/b000000x
Non-luminous
precursor,
2-(1-pyrenyl)-9,10-dihydro-9,10-
ethanoanthracene-11,12-dione, was photochemically converted to
10 highly-fluorescent 2-(1-pyrenyl)anthracene quantitatively in
solution and in PMMA film and the fluorescence quantum yield
of the acene in benzonitrile was as high as 0.99.
Fluorescent molecular probes are of great interest due to their
versatile applications in chemical, environmental and
15 biological science. Fluorescence is one of the most promising
tools for the detection of small amounts of molecules, since
fluorescence can even be detected in only one molecule and is
applied in various areas such as microanalysis,1 bioimaging2
and memory media.3 Recently an efficient conversion of non-
20 luminous molecules to highly-fluorescent molecules by
external stimuli like heat or light have received attention due
to their potential for the application in optical memory media,
fluorescence imaging and super-resolution fluorescence
imaging.4-10 In this context, one-way conversion would be
25 desirable for read-only memory and single-molecule
microscopy.
Scheme 1. Photoconversion from α-diketone to pyrenylanthracenes.
55 yield was only 3 % due to its low solubility. Py-3-Ant can be
also prepared by Sonogashira couplung from 1 and 1-
ethynylpyrene in 12%, but the purification on silica gel
column chromatography was difficult because of the low
solubility and close Rf values with byproducts. To solve the
60 solubility problem, the precursors PyDK and Py-3-DK were
prepared as shown in Scheme 2. 2-Bromoanthracene 1 was
reacted with vinylene carbonate by Diels-Alder reaction to
give adduct 2 in 76% yield. The compound 2 was coupled
with pyreneboronic acid by Suzuki-Miyaura coupling to give
65 adduct 3a in 51% yield. The obtained adduct 3a was
hydrolyzed to give diol compound 4a in 74% yield, followed
by Swern oxidation to give PyDK in 14% yield. Py-3-DK was
also prepared using 2-ethynylpyrene as shown in Scheme 2.
Pyrene is a versatile blue-fluorophore with high fluorescence
quantum yields. Aryl-pyrene compounds are one of the highly
fluorecent materials,11 but unfortunately their solubility in
30 common organic solvent is quite low and the purification is
difficult. In this regard
a
photochemical quantitative
conversion of 9,10-dihydro-9,10-ethanoanthracene-11,12-
dione (DK) to anthracene (Ant) is an useful one-way reaction
in solution or film (Scheme 1)12. This reaction has recently
35 been applied to the photochemical synthesis of pentacene13
and its relatives for the fabrication of FET devices by a
solution process14, and for the protecting groups to prepare
air-unstable substituted pentacenes15 and larger acenes16
.
Furthermore we found the diketome moities can work as an
40 intramolecular quncher of the fluorophore for the substited
tetracene compounds, resulting the in-situ photochemical
conversion from a non-fluorescent precursor to a fluorescent
compound.17 In connection with these results, this
photoconversion will be ideal for the synthesis of highly pure
45 and highly fluorescent aryl-pyrene compounds from soluble
and non-luminous precursors. We report here an in situ
quantitative preparation of highly blue-fluorescent pyrene-
anthracene dyes (PyAnt and Py-3-Ant) from non-luminous α-
70 Reagents and conditions: i) vinylene carbonate, xylene, autoclave,
180 °C, 3 d, 76%; ii) for 3a, pyreneboronic acid, Pd(PPh3)4, Na2CO3,
1,4-dioxane, reflux, 18 h, 51%; iii) for 3b, 2-ethynylpyrene, CuI,
Et3N, Pd(PPh3)4, toluene, reflux, 18 h, 34%; iv) K2CO3, THF,
methanol, H2O, rt, overnight, 74% for 4a and 61% for 4b; v) TFAA,
75 dry-DMSO, N,N-(iso-pro)2EtN, dry-CH2Cl2, 1.5 h, 14% for PyDK
and 60% for Py-3-DK.
diketone
precursors
(PyDK
and
Py-3-DK)
upon
Scheme 2. Syntheses of PyDK and Py-3-DK.
50 photoirradiation in solution and in film (Scheme 1).
PyAnt can be prepared by Suzuki-Miyaura coupling of 2-
bromoanthracene (1) and pyreneboronic acid, however the
The UV-vis absorption and fluorescence spectra of PyAnt and
PyDK in toluene are shown in Figure １ . PyAnt has an
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absorption peak at 349 nm (
shoulders at both sides in toluene. The emission peaks were 35 moiety (Figure 1 and ESI†, Figure S5).
observed at 443 and 478 nm with the fluorecence quantum The similar tendancy was observed for Py-3-Ant and Py-3-
yield ( f) of 0.86 in toluene. The fluorescence peak (443 nm)
ε
= 4.50 × 104 M-1cm-1) with
to the quenching of the excited state of pyrrene by diketone
Φ
DK. UV-vis absorption spectrum of Py-3-Ant showed four
peaks at 308, 365, 393 and 418 nm in toluene (ESI†, Figures
S3 and S6). Due to the triple bonds between pyrene and
5
of PyAnt showed red-shift by 68 nm from parent pyrene due
to the through-bond interaction between pyrene and
anthracene moieties. The absorption spectra were similar in 40 anthracene moieties, the π-conjugation of Py-3-Ant expanded
toluene, CH2Cl2, benzonitrile, and DMSO, but the
fluorescence of PyAnt showed solvatochromic shift as shown
more than that of PyAnt, which gave the red-shift of the
absorption spectra. Fluorescence spectra of Py-3-Ant also
showed the solvent effects: λem = 426, 450 and 482 nm in
toluene (Φf = 0.90); 485 nm in CH2Cl2 (0.92); 488 nm (0.94)
10 in Table 1 and ESI†, Figure S1. The fluorescnece peaks (λem
)
gave bathochromic shifts by increasing the polarity of the
solvents: λem = 443 nm (Φf = 0.86) in tolunene, 486 nm 45 in PhCN: 497 nm (0.95) in DMSO. The fluorescence lifetimes
(0.92) in CH2Cl2, 486 nm (0.99) in PhCN, and 496 nm (0.91)
in DMSO. These result are well coincident with the known
15 superposition of a nonpolar locally excited (LE) and a
strongly polar charge transfer (CT) contribution of substituted
(τf) were also measured (Table 1 and ESI†, Figure S7). Py-3-
Ant showed single-exponential decays due to the rigid linkage
with a triple bond.
To investigate the photocleavage reaction of PyDK, the
pyrene compounds.11 The fluorescence lifetimes ( f) were also 50 photoconversion was monitored by 1H NMR spectroscopy
τ
measured (Table 1 and ESI†, Figure S2). Since the rotary
motion around the C-C linkage between pyrene and
20 anthracene is possible, PyAnt showed bi-exponential decay in
CH2Cl2, PhCN, and DMSO.
under an argon atmosphere (ESI†, Figure S8). PyDK was
placed in degassed CDCl3 and irradiated at 470 nm with a
xenon light source through monochromater (14.9 mW/cm2).
During the photoconversion, the singlet peaks at 5.1 and 5.2
55 ppm due to bridge-head protons of PyDK gradually decreased
while peaks of peri-positions of PyAnt increased at 8.5 ppm.
After 25 min the photoconversion finished without giving any
1
by-products. The H NMR spectrum at 25 min was identical
with the spectrum of PyAnt, directly prepared by Suzuki-
60 Miyaura coupling of
1 and pyreneboronic acid. The
photoreaction of Py-3-DK to Py-3-Ant also proceeded
successfully (ESI†, Figure S8).
The change in UV-vis absorption spectra during the
photolysis of PyDK was monitored. When PyDK was
65 irradiated at 468 nm (1.86 mW/cm2), the decarbonylation
occurred giving the corresponding PyAnt (ESI†, Figure S9).
The relative quantum yield of the photoconversion reaction of
PyDK excited at 468 nm was 0.29, compared to the absolute
quantum yield of DK (0.37). The photoreactions of PyDK
70 was also performed by excitation at π-π* absorption of pyrene
moieties (370 nm, < 0.88 mW/cm2), monitored by the spectra
change of the absorption and fluorescence in toluene (Figures
2). During the irradiation, the blue fluorescence increased,
since PyDK was not fluorescent while PyAnt was strongly
75 fluorescent. The same phenomenum was also observed for Py-
3-DK and Py-3-Ant and the relative quantum yield of the
photoconversion reaction of Py-3-DK was 0.27 (ESI†, Figure
S9 and S10).
Figure 1. The absorption (solid lines) and fluorescence (dashed lines)
spectra of PyDK (black) and PyAnt (red) in toluene; excited at 380 nm.
25 PyDK has the peak of pyrene moiety at 348 nm (
104 M-1cm-1) in toluene and the absorption of diketone moiety
at 461 nm (
= 7.40 × 102 M-1cm-1). The absorption at 461 nm
ε = 2.71 ×
ε
is similar with the absorption of non-substituted DK (ESI†,
Figure S3) but absorption of PyDK at 461 nm is slightly
30 larger than that of DK due to the overlap of CT-like
absorption from pyrene moiety to carbonyl moiety, as
predicted by TD-DFT calcuration (ESI†, Figures S4). PyDK
was non-fluoresocent with excitation at 380 and 460 nm due
Table 1 Absorption and fluorescence peaks (λabs and λflu), fluorescence quantum yields (Φf), and fluorescence lifetimes (τf) of PyAnt and Py-3-Ant
in various solventsa.
flu /nma
Φfb
0.86
0.92
0.99
0.91
0.90
0.92
0.94
0.95
τf /ns (A)c
χ2
Compounds
Solvents
λ
abs /nm
λ
PyAnt
Toluene
CH2Cl2
PhCN
DMSO
Toluene
CH2Cl2
PhCN
2.38
8.93
25.2
46.5
2.38
8.93
25.2
46.5
349
348
352
351
443, 478
486
4.22
1.64
1.33
1.39
1.11
1.68
1.52
1.14
1.40
4.26 (0.46) 6.71 (0.54)
4.79 (0.85) 8.78 (0.15)
4.47 (0.61) 7.69 (0.39)
1.98 (0.99) 6.74 (0.01)
2.85
486
496
Py-3-Ant
308, 365, 393, 418
306, 364, 391, 416
310, 366, 397, 420
308, 367, 397, 421
426, 450, 482
485
488
497
2.96
DMSO
3.56 (0.92) 5.59 (0.08)
a dielectric constant; bλflu and Φf were measured by excitation at 380 nm. c τf was measured by excitation at 366 nm.
2
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30 measurement. The authors also thank Mr. Leigh McDowell for
checking the English in the manuscript. This work was partly
supported by Grants-in-Aid (No. 22350083 to H. Y.) and the
Green Photonics Project in NAIST sponsored by the Ministry
of Education, Culture, Sports, Science and Technology,
35 MEXT, Japan.
Notes and references
a Graduate School of Materials Science, Nara Institute of Science and
Technology, Ikoma 630-0192, Japan
bDepartment of Chemistry and Biology, Graduate School of Science and
40 Engineering, Ehime University, Matsuyama 790-8577, Japan
cCREST, JST, Chiyoda-ku 102-0076, Japan
† Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/b000000x/
45 ‡ Footnotes should appear here. These might include comments relevant
to but not central to the matter under discussion, limited experimental and
spectral data, and crystallographic data.
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Figure 2. (a) The change in (a) absorption spectra (5.6 × 10-5 M) and (b)
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PyDK in toluene.
λ
ex = 370 nm) of
50
55
60
3
4
5
Finally we have performed the photoconversion of PyDK and
Pt-3-DK in PMMA film, as shown in Figure 3 and ESI†,
Figure S11. After the photoirradiation over >390 nm for 10
5
min, the
Φf of Py-Ant was incresed to 0.23. For the PyDK
6
7
film fluorecence was also observed around 420 nm with Φf
10 less than 0.02, which belonged to Py-Ant generated during
the measurement. This result indicates PyDK in film is highly
sensitive to the light and the photoconversion from PyDK to
8
9
Py-Ant occurred during the measurement. The
Φf of PMMA
film of Py-3-Ant prepared by this photoconversion was 0.11.
15
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Figure 3. Absorption and emission spectra of PyDK (black) and PyAnt
(red) in PMMA film; excited at 380 nm.
Conclusions
20 We have succeeded in preparing the PyDK and Py-3-DK as
latent fluorophores which can be effectively converted to
highly blue-fluorescent
PyAnt
and
Py-3-Ant
by
photoirradiation in soliution and in film. The one-way
convertible precursors of highly-fluorescent fluorophores will
25 be promising for the various applications in the areas of
microanalysis and memory media.
Acknowledgment The authors thank Ms. Mika Yamamura
and Ms. Yuriko Nishiyama for the measurement of mass
spectra and Mr. Yasuo Okajima for the fluorescnece lifetimes
17 T. Aotake, Y. Yamashita, T. Okujima, N. Shirasawa, Y. Jo, S.
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