Catalytic Annulation of Alkynyl 1,2-Diketone Leading to Hydroxy Spirocyclopenteneindenedione: An Organic Dye with Strong Crystallization-Induced Emission and Data Storage Application

Article abstract of DOI:10.1021/acs.orglett.0c00581

An unprecedented cascade annulation between alkynyl 1,2-diketones and indene-1,3-diones is achieved for the first time, leading to a series of propeller-like large conjugated compounds in ≤99% yield. The products show strong crystallization-induced emissi

Full text of DOI:10.1021/acs.orglett.0c00581

pubs.acs.org/OrgLett
Letter
Catalytic Annulation of Alkynyl 1,2-Diketone Leading to Hydroxy
Spirocyclopenteneindenedione: An Organic Dye with Strong
Crystallization-Induced Emission and Data Storage Application
∥
∥
Zhizhou Chen, Fang Yu, Rui Liu, Xiangling Lin, Shuang Yang, Jinggong Liu,* Bolai Chen,*
Sakkani Nagaraju, Min Zeng, Chenglin Ding, and Xinqiang Fang*
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ABSTRACT: An unprecedented cascade annulation between
alkynyl 1,2-diketones and indene-1,3-diones is achieved for the
first time, leading to a series of propeller-like large conjugated
compounds in ≤99% yield. The products show strong crystal-
lization-induced emission, with the colors changing from green to
red. The fluorescence of the dye can be switched on and off by
external acid/alkali stimuli, which can be utilized to develop a
practical technology for rewritable information storage and security
ink.
eveloping novel reactions leading to organic dyes with
unique photophysical properties and multiple applica-
Scheme 1. Synthesis of the Fluorescent Dyes via Ynone-
Mediated Annulations
D
tions is one of the ultimate goals for chemists. For instance,
fluorescent materials have attracted considerable attention
owing to their wide applications in organic light-emitting
diodes (OLEDs), semiconductor lasers, and fluorescent
1
sensors. However, the notorious aggregation-caused quench-
ing (ACQ) problem has greatly restricted their practical
applications because fluorescent materials are usually used in
2
the aggregated or solid state. Therefore, the search for
materials with aggregation- or crystallization-induced emission
(
AIE or CIE, respectively) characteristics serves as an excellent
3
solution for the ACQ challenge. Moreover, smart luminescent
materials have promising uses in optical data recording, data
security, and data protection because their emission responds
4
to stimuli. However, despite the great application potential of
the organic dyes with these unique properties, the discovery of
new classes of functional molecules with all of the valuable
characteristics mentioned above is still challenging and thus
highly desired.
disclosing various new reactivities associated with α-diketones
and their derivatives, including alkynyl diketones. In this
regard, we surveyed the reaction between alkynyl α-diketones
and indene-1,3-diones. To our surprise, a series of unexpected
On the contrary, annulation reactions mediated by ynones
have been established as a powerful tool in organic synthesis
8
5
and related fields. However, to the best of our knowledge,
limited research attention has been paid to the construction of
functional materials with various potential applications such as
̈
organic dyes. In this context, Muller and co-workers system-
atically developed the rapid synthesis of a series of
Received: February 13, 2020
fluorophores using ynones formed via the coupling of acyl
6
chlorides and alkynes. The study is valuable in various fields,
and some selected reactions are shown in Scheme 1a. We have
7
been interested in α-diketone chemistry, with the aim of
©
XXXX American Chemical Society
https://dx.doi.org/10.1021/acs.orglett.0c00581
A
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products, formed probably via an unprecedented Michael
addition−aldol reaction−condensation sequence, were ob-
tained. For comparison, Li and co-workers have reported the
ring expansion reactions of ynones and indene-1,3-dione,
leading to thoroughly different benzoannulated seven-mem-
bered rings. To our delight, the novel propeller-like large
conjugated structure of the products obtained in this work
enables the product possessing unique photoelectronic and
chemical properties, such as CIE, and can be switched between
on and off states by external acid/base stimuli (Scheme 1b).
All of these considerations show the protocol has potential
value in diverse fields (e.g., OLEDs, data security storage, etc.).
Although molecules made by diketone-mediated annulation
reactions have been extensively studied, examples furnishing
organic dyes with the properties described above are rarely
revealed. Herein, we report our results.
acetone (Table 1, entries 7−9, respectively). Considering that
dehydration occurs during the reaction, we added some
additives such as MgSO and Na SO to the reaction system.
Compared to the previous conditions, the yield of 3a was
obviously improved (Table 1, entries 10 and 11). Then further
4
2
4
5
e
increasing the amount of MgSO to 800 mg afforded 3a in a
4
practical yield of 84% (Table 1, entry 12), and increasing the
reaction time could further enhance the yield (Table 1, entry
13). Slighly increasing the dose of 2a was found to be
beneficial for enhancing the yield of 3a (Table 1, entry 14), but
decreasing the amount of DBU proved to be deleterious to the
reaction (Table 1, entry 15). Finally, the yield of 3a could be
promoted to a high level of 99% using 2.2 equiv of 2a, 0.3
equiv of DBU, and a reaction time of 24 h (Table 1, entry 16).
Under the optimized reaction conditions, the substrate
scope with respect to both ynedione 1a and indandione 2a was
investigated to evaluate the generality of the reaction. The
As shown in Table 1, we commenced by checking the
reaction of alkynyl α-diketone 1a and indandione 2a in the
2
variation of the R group at the alkynyl moiety was checked
first. The introduction of 4-OMe-, 4-F-, or 2-F-substituted
phenyl rings into the substrates had little effect on the
outcomes, leading to 3b, 3c, and 3d in 82%, 77%, and 86%
yield, respectively (Scheme 2, 3b−3d, respectively). In
particular, when the substituent is a naphthyl or natural
product derivative, the reaction still worked well to give 3e and
a
Table 1. Optimization of the Reaction Conditions
3
f in 51% and 74% yields, respectively (Scheme 2). To our
2
delight, when R is an aliphatic group, the reaction proceeded
smoothly, delivering 3g in an excellent 93% yield (Scheme 2).
Furthermore, 4-Br-, 4-Me-, and 3-Me-substituted phenyl rings
time
(h)
yield
b
entry
catalyst
solvent temp additive
(%)
1
1
K CO3
TMEDA
DMAP
CH Cl
rt
rt
rt
rt
rt
rt
rt
rt
rt
rt
rt
rt
rt
rt
rt
rt
−
−
−
−
−
−
−
−
−
5
5
5
5
5
5
5
5
5
5
5
5
12
12
12
24
46
43
35
43
50
63
5
can be used as the R group in the diketone substrates,
2
2
2
2
2
2
2
2
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
CH Cl
producing the corresponding products in good to excellent
2
CH Cl
2
yields (Scheme 2, 3h−3j, respectively). To our delight, other
1
KHMDS
CH Cl
2
R groups such as carbazolyl, biphenyl, and naphthyl were all
Et N
CH Cl
3
2
tolerated in this reaction (Scheme 2, 3k−3m, respectively).
1
2
DBU
DBU
DBU
DBU
DBU
DBU
DBU
DBU
DBU
DBU
DBU
CH Cl
2
Gratifyingly, variation of both R and R groups using
differently substituted phenyl rings proved to be possible,
allowing access to 3n−3s in 69−99% yields (Scheme 2).
Finally, we checked the scope of indandione substrates by
installing electron-withdrawing or electron-donating groups
and found that the reactions can still give rise to the
corresponding products, albeit with lower yields (Scheme 2,
3u and 3v). The configuration of the products was determined
via single-crystal X-ray structure analysis of 3a and 3b, and
other products were assigned by analogy (Figure 3a). A
propeller-like structure with a conjugated system and intra-
molecular hydrogen bonding can be clearly seen from the
images of the crystals.
The postulated mechanism is shown in Figure 1. Initially,
the Michael addition of 2a to 1a leads to the formation of
intermediate I, which is followed by a proton transfer to
produce II. The aldol reaction within II affords spirocyclo-
pentenone III, and the condensation between III and 2a gives
product 3a. The whole process contains the formation of two
C−C bonds and one C = C bond.
THF
toluene
acetone
CH Cl
32
7
c
0
1
2
3
4
5
6
MgSO4
74
72
84
91
93
84
99
2
2
2
2
2
2
2
2
c
CH Cl
Na SO
2
2
4
d
d
d
d
d
CH Cl
MgSO4
MgSO4
MgSO4
MgSO4
MgSO4
2
CH Cl
2
,
,
,
e
CH Cl
2
f
CH Cl
2
e
,
f
CH Cl
2
a
Reaction conditions: 1a (0.1 mmol), 2a (0.2 mmol), catalyst (0.05
b
mmol), solvent (2 mL), under argon protection, 5 h, rt. Isolated
yields based on 1a. An additive (200 mg) was added. MgSO (800
mg) was added. 2a (0.22 mmol) was used. A base (0.03 mmol) was
used.
c
d
4
e
f
presence of 50 mol % K CO . As mentioned above, no simple
2
3
Michael addition, aldol reaction, or condensation products
were detected. Instead, an unexpected annulation product 3a,
formed probably via a Michael addition−aldol reaction−
condensation sequence, was obtained in 46% yield (Table 1,
entry 1). To improve the yield, we then tested a series of other
bases such as tetramethylethylenediamine (TMEDA), DMAP,
and KHMDS but did not observe satisfying results (Table 1,
Having obtained a number of propeller-like twisted organic
molecules, we went on to investigate their photophysical
properties. Product 3a in solution and in amorphous form does
not show emission, but strong emission was detected when it is
in its crystal form. This indicates the CIE property of the
molecules. Inspired by this observation, we selected some
other samples bearing different substituents, with the purpose
of tuning and switching the solid-state fluorescence, owing to
its importance both in fundamental research and in industrial
entries 2−4, respectively). The survey of Et N resulted in 3a in
5
3
0% yield (Table 1, entry 5), and when DBU was used as the
base, the yield of 3a could be improved to 63% (Table 1, entry
). Further solvent screening using DBU suggested that
CH Cl was still the best compared to THF, toluene, and
6
9
applications. As displayed in Figure 2, the crystalline solids of
2
2
B
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a
Scheme 2. Substrate Scope
Figure 2. Selected illuminant compounds under visible light and
ultraviolet irradiation at 365 nm.
emission behavior in the crystalline state is probably caused by
the hydrogen bonding, which stabilizes the molecular structure
and blocks the molecular vibration. This is beneficial for the
regular packing of the molecule and the induction of emission
9
(
Figure 3b,c). In contrast, compounds 3 in solution and
Figure 3. (a) Single-crystal X-ray structures of 3a and 3b. (b)
Molecular packing arrangement in the crystal of 3a. (c) Molecular
packing arrangement in the crystal of 3b.
amorphous form probably contain molecular structures that
can undergo conformational change rapidly, which results in
energy dissipation. We also tested the absorption and emission
spectra of the organic dyes mentioned above (see Figures S1−
S3 and Table S3). The UV−vis absorption peak of solid
molecules 3 ranged from 420 to 592 nm, and the fluorescence
emission ranged from 529 to 663 nm correspondingly. The
a
All reactions were run on a 0.1 mmol scale; all yields were of isolated
products.
blue-shift of the absorption spectra tested in CH CN is
3
probably caused by solvation.
Additionally, we rationalized that the intramolecular hydro-
gen bonding plays vital roles in generating fluorescence, and
the proton from the OH group possesses high acidity, which
probably enables the fluorescence of the dyes to switch on and
off upon acid/alkali stimuli (Figure 4a). Therefore, the
material can be utilized as a security ink to design a simple
encrypting/decrypting technology and to realize data secure
storage. Unlike other complicated technologies requiring
Figure 1. Postulated mechanism.
10
3
c, 3h, 3a, 3b, 3j, 3r, and 3p show fluorescent emission in the
green, yellow, orange, and red regions when they are subjected
to ultraviolet (UV) irradiation at 365 nm. The origin of the
background or mask fluorescence, this technique is simple
and easily operable. In this case, a piece of ivory board was
chosen as the blank medium owing to its weak emission
C
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Letter
Chemistry, Center for Excellence in Molecular Synthesis, Fujian
Institute of Research on the Structure of Matter, University of
Chinese Academy of Sciences, Fuzhou 350100, China;
orcid.org/0000-0001-8217-7106; Email: xqfang@
fjirsm.ac.cn
Jinggong Liu − Orthopedics Department, Guangdong Provincial
Hospital of Traditional Chinese Medicine, The Second Affiliated
Hospital of Guangzhou University of Chinese Medicine,
Guangzhou 510120, China; Email: liujinggong001@163.com
Bolai Chen − Orthopedics Department, Guangdong Provincial
Hospital of Traditional Chinese Medicine, The Second Affiliated
Hospital of Guangzhou University of Chinese Medicine,
Guangzhou 510120, China; Email: chenbolai337@163.com
Figure 4. Photographs of the luminescence of security writing under
UV light at 365 nm.
Authors
Zhizhou Chen − Key Laboratory of Coal to Ethylene Glycol and
Its Related Technology and State Key Laboratory of Structural
Chemistry, Center for Excellence in Molecular Synthesis, Fujian
Institute of Research on the Structure of Matter, University of
Chinese Academy of Sciences, Fuzhou 350100, China
Fang Yu − Key Laboratory of Coal to Ethylene Glycol and Its
Related Technology and State Key Laboratory of Structural
Chemistry, Center for Excellence in Molecular Synthesis, Fujian
Institute of Research on the Structure of Matter, University of
Chinese Academy of Sciences, Fuzhou 350100, China
Rui Liu − Key Laboratory of Coal to Ethylene Glycol and Its
Related Technology and State Key Laboratory of Structural
Chemistry, Center for Excellence in Molecular Synthesis, Fujian
Institute of Research on the Structure of Matter, University of
Chinese Academy of Sciences, Fuzhou 350100, China
Xiangling Lin − Fuzhou University, Fuzhou 350116, China
Shuang Yang − Key Laboratory of Coal to Ethylene Glycol and
Its Related Technology and State Key Laboratory of Structural
Chemistry, Center for Excellence in Molecular Synthesis, Fujian
Institute of Research on the Structure of Matter, University of
Chinese Academy of Sciences, Fuzhou 350100, China
(
Figure 4b-I). As shown in Figure 4, the word “FJIrsm” was
written on the paper by using the mixture of 3a and TEA as the
ink. Because the ink has no fluorescence, the word is invisible
in both daylight and UV light (Figure 4b-II). Because the word
stored on the paper is in a nonfluorescent form, no extra
encryption technologies are needed. To decrypt the data, the
test paper is exposed in TFA vapor, and then the green
fluorescence of the word “FJIrsm” is revealed clearly owing to
the precipitation of the crystalline 3a (Figure 4b-III). We
believe that this security ink should have potential application
11
in security data storage for its simple and reliable operation.
In summary, we have developed a new class of organic dyes
through an unprecedented cascade annulation between alkynyl
α-diketones and 1,3-indandiones. The reaction affords a series
of propeller-like molecules with large conjugated structures in
≤
99% yield. Moreover, the unique structure enables the
products to have specific photophysical and chemical proper-
ties. When the substituents are switched, the fluorescent
emission of the crystalline molecules can vary from green to
red, which displays obvious CIE. The unique structure also
makes the material have the property of on/off fluorescence
switching, which can be used as the security ink to achieve
simple encrypting/decrypting technology, and to realize data
secure storage. Further detailed photophysical and computa-
tional studies to thoroughly elucidate the unusual lumines-
cence behavior are ongoing in our group and will be reported
in due course.
Sakkani Nagaraju − Key Laboratory of Coal to Ethylene Glycol
and Its Related Technology and State Key Laboratory of
Structural Chemistry, Center for Excellence in Molecular
Synthesis, Fujian Institute of Research on the Structure of
Matter, University of Chinese Academy of Sciences, Fuzhou
3
50100, China
Min Zeng − Fuzhou University, Fuzhou 350116, China
Chenglin Ding − Fuzhou University, Fuzhou 350116, China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.orglett.0c00581
ASSOCIATED CONTENT
■
*
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.orglett.0c00581.
Author Contributions
∥Z.C. and F.Y. contributed equally to this work.
Experimental procedures and spectroscopic data for all
new compounds (PDF)
Notes
Accession Codes
The authors declare no competing financial interest.
CCDC 1965886−1965887 contain the supplementary crys-
tallographic data for this paper. These data can be obtained
free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by
emailing data_request@ccdc.cam.ac.uk, or by contacting The
Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
ACKNOWLEDGMENTS
■
This work was supported by the NSFC (21871260, 21502192,
and 21402199), the Strategic Priority Research Program of the
Chinese Academy of Sciences (XDB20000000), the Fujian
Natural Science Foundation (2018J05035), and the China
Postdoctoral Science Foundation (2018M630734). The
authors thank Prof. Qing-Fu Sun, Prof. Tianfu Liu, Prof.
Qianchong Zhang, and Dr. Meijuan Han of the Fujian Institute
of Research on the Structure of Matter for valuable discussion.
AUTHOR INFORMATION
Corresponding Authors
■
Xinqiang Fang − Key Laboratory of Coal to Ethylene Glycol and
Its Related Technology and State Key Laboratory of Structural
D
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Letter
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era, C.;
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