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Accepted Manuscript
Highly efficient halochromic behaviors in solution and film states with 9,19dichloro-5,15-dihydrocarbazolo[3′,4':5,6][1,4]oxazino[2,3-b]indolo[3,2-h]phenoxazine
derivative
Young Un Kim, Gi Eun Park, Suna Choi, Chang Geun Park, Min Ju Cho, Dong Hoon
Choi
PII:
S0143-7208(18)30614-4
DOI:
10.1016/j.dyepig.2018.08.030
Reference:
DYPI 6944
To appear in:
Dyes and Pigments
Received Date: 20 March 2018
Revised Date:
28 June 2018
Accepted Date: 19 August 2018
Please cite this article as: Kim YU, Park GE, Choi S, Park CG, Cho MJ, Choi DH, Highly efficient
halochromic behaviors in solution and film states with 9,19-dichloro-5,15-dihydrocarbazolo[3′,4':5,6]
[1,4]oxazino[2,3-b]indolo[3,2-h]phenoxazine derivative, Dyes and Pigments (2018), doi: 10.1016/
j.dyepig.2018.08.030.
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to
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Graphical abstract
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DOI: 10.1002/ ((please add manuscript number))
Article type: Full Paper
Highly Efficient Halochromic Behaviors in Solution and Film States with
b]indolo[3,2-h]phenoxazine Derivative
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9,19-Dichloro-5,15-dihydrocarbazolo[3',4':5,6][1,4]oxazino[2,3-
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Young Un Kim, Gi Eun Park, Suna Choi, Chang Geun Park, Min Ju Cho* and Dong Hoon Choi*
Department of Chemistry, Research Institute for Natural Sciences, Korea University, 145 Anam-ro,
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Sungbuk-Gu, 02841 Seoul, Republic of Korea.
Corresponding authors: Min Ju Cho (E-mail: chominju@korea.ac.kr); Dong Hoon Choi (E-mail:
dhchoi8803@korea.ac.kr)
Abstract:
We
demonstrated
9,19-dichloro-5,15-bis(2-decyltetradecyl)-5,15-
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dihydrocarbazolo[3',4':5,6][1,4]oxazino[2,3-b]indolo[3,2-h]phenoxazine (DTD-CzDxz) as a
new halochromic compound with a prominent UV-vis absorption spectral response under
acidic conditions. DTD-CzDxz was constructed with branched alkyl chains at the ends of a
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planar fused molecule to achieve good solubility in common organic solvents. When the
nitrogen in the oxazine ring was diprotonated, the entire absorption spectrum shifted from the
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visible region to the near-infrared (NIR) region for both solution and film states. Owing to a
significant red shift of 256 nm in the solution state, the color of the sample quickly faded and
the sample became colorless and transparent and could be easily recognized by the naked eye.
In addition, the photoluminescence spectrum of DTD-CzDxz displayed significantly
weakened emission intensity at 650 nm under acidic condition. When triethylamine was
added into the acid-treated solution, the emission intensity at 650 nm was restored to its
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initial value. The neat DTD-CzDxz film was transparent and colorless film when exposed to
acid vapors. However, the absorption spectrum reverted to its original form as soon as the
film was exposed to air at room temperature. The efficient cyclizability due to the
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halochromism of the DTD-CzDxz film showed that there was no significant degradation in
the absorption intensity at 567 and 794 nm. Hence, it could be concluded that DTD-CzDxz is
a good candidate for solid-state halochromic sensors that can operate under both acidic and
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basic conditions.
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Keywords: dye, dioxazine, halochromism, NIR absorption, pH sensor, acid vapor sensor
1. Introduction
Organic dyes and pigments are major colorants containing specific chromophores and are
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used to color other materials. [1-5] Apart from being used as colorants, they are used in
optical components, semiconductors, and various sensors, owing to their conjugated
structures. [6-10]
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The specific dyes and pigments used in sensor applications should have unique
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characteristics that enable them to display varied functions when they selectively interact
with target analytes through π-conjugation. It is known that long π-conjugation in planar
molecules originate from polycyclic and acene- type compounds consisting of fused aromatic
rings. Among the various acenes, heteroatoms including sulfur, nitrogen and oxygen have
been used for forming heteroaromatic fused ring compounds. [11-13] In particular, nitrogen is
highly effective for maintaining the aromatic structural stability under most conditions,
including ambient conditions and its reactivity as an active site for possible reactions such as
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alkylation and protonation. [14-16]
As ionic or hydrogen bonds can be formed with nitrogen, the electron distribution of Ncontaining heteroaromatic compounds is expected to change on exposure to a hydrogen ion
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environment, i.e., acidic conditions. Therefore, heteroaromatic compounds with nitrogen
atoms may exhibit halochromism, i.e., due to change in pH, because the incorporation of
nitrogen for quaternization [17-18] can allow the manipulation of frontier molecular orbital
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energies and electrical conductivity. The quaternized nitrogen also facilitates intermolecular
interactions through ionic interactions in solution and solid-states. Reynolds et. al. reported
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pronounced halochromism in N-containing heteroaromatic compounds that displayed a
significant color change (from 450 to 750 nm) with a remarkably high absorption spectral
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shift of 300 nm. [19]
Fig. 1. Molecular structures of DTD-CzDxz and DTD-CzDxz (2H+) and solution images in
chloroform.
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Garino et. al. and Ando et. al. also demonstrated a large Stokes shifts of 174 nm (from 304 to
478 nm) and of 120 nm (from 316 to 436 nm) for tetradentate polyazines based on
imidazo[1,5-a]pyridine and N,N′-dicyclohexyl-3,6-dihydroxypyromellitimide, respectively,
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owing to the halochromic effect. [20-21]
In this study, we synthesized an N-containing heteroaromatic acene compound DTDCzDxz, based on the bluish purple pigment carbazole dioxazine (CzDxz). The mother
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structure of DTD-CzDxz has long been used as a pigment-type colorant and therefore, its
solubility should be improved for further application in film-based device fabrications.
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Through the modification of the molecular structure of DTD-CzDxz by attaching alkyl
chains (e.g. decyltetradecyl) at two carbazole sides, its solubility is improved to convert it
into a soluble dye molecule. CzDxz comprised five fused rings in a row with two oxazine
rings. The oxazine rings and the position of the nitrogen atoms well resemble the structure of
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N-heteroaromatic acene compounds exhibiting effective halochromism. The properties of
CzDxz have been investigated in detail previously. [22-23] However, the optical
characteristics of N-heteroaromatic acenes with nine fused rings and continuous π-
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conjugation has been scarcely reported, which makes the current study important. Although a
spectral shift is recognized as a common feature in chromic sensors, most shifts lead to a
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color change within the visible region. [24-26] However, only a few studies have reported
color bleaching in known halochromic compounds. [27]
Both the solution and film states of DTD-CzDxz showed a bluish purple color in their
absorption spectrum, which is close to the near infrared (NIR) wavelength range. When acid
species was added to the solution or when the thin film was exposed to acid vapor, the
absorption spectra remarkably shifted to the NIR wavelength range, leading to the
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disappearance of the visible color in both solution and film states. Furthermore, when
triethylamine (TEA) was added to an acid-containing solution of DTD-CzDxz, the absorption
spectrum of the solution showing NIR absorption returned to its original form. In addition,
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the acid-treated thin film returned to its original color upon exposure to air, suggesting DTDCzDxz to be an excellent material for acid vapor sensors using solid-state films.
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2. Experimental
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2.1 Materials and synthesis
All commercially available starting materials and solvents were purchased from Sigma
Aldrich Chemical Co., Alfa Aesar Co., or Tokyo Chemical Industry Co., and were mostly
used as-received. For specific reactions, the purchased chemicals were purified where
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necessary. Carbazole was purchased from Alfa Aesar Co. Compounds 1, 2, and 3 were
2.2 Synthesis
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synthesized using previous methods with some modifications. [28-30]
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2.2.1. Synthesis of 2,5-dichloro-3,6-bis((9-(2-decyltetradecyl)-9H-carbazol-3yl)amino)cyclohexa-2,5-diene-1,4-dione, (4)
Compound 3 (4 g, 9.84 mmol) was dissolved in ethanol (50 mL). The solution was poured
dropwise into a three-necked round bottom flask after adding chloranil (1.14 g, 4.68 mmol)
and potassium acetate (0. 97g, 9.84 mmol) under argon atmosphere. The reaction mixture was
stirred for 4 h at 65 °C. After cooling to 25 °C, the mixture was extracted with
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dichloromethane and additional water, and then evaporated in a vacuum evaporator to obtain
3.5 g (75.8%) of compound 4 as a solid violet product. 1H NMR (500 MHz, CDCl3, δ, ppm):
8.73 (s, 2H), 8.09 (d, J = 7.1 Hz, 2H), 7.91 (s, 2H), 7.52 (t, J = 7.4 Hz, 2H) , 7.39 (d, J = 8.5
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Hz, 2H), 7.37 (d, J = 8.5 Hz, 2H), 7.25-7.32 (m, 4H), 4.20 (d, J = 7.1 Hz, 4H), 2.14 (s, 2H),
1.25 (m, 80H), 0.87 (d, J = 6.9 Hz, 12H). Elemental analysis: anal. calcd for C78H114Cl2N4O2
(%): C, 77.38; H, 9.49; Cl, 5.86; N, 4.63; O, 2.64. Found: C, 77.40; H, 9.46; N, 4.66.
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MALDI−TOF−MS (m/z): calcd for C78H114Cl2N4O2: 1210.67; found: 1211.83 [M]+
2.2.2. Synthesis of 9,19-dichloro-5,15-bis(2- decyltetradecyl)-5,15-dihydrocarbazolo
[3',4':5,6][1,4]oxazino[2,3-b]indolo[3,2-h]phenoxazine, (DTD-CzDxz)
A methanol solution (60 mL) containing potassium acetate (1.05 g, 10.65 mmol) was added
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to a mixture of compound 4 (3 g, 3.04 mmol) and dimethylhydrofuran (30 mL) under
nitrogen. After adding (diacetoxy)iodobenzene (2.74 g, 8.52 mmol) dropwise, the mixture
was stirred for 3 h at 25 °C. Then, the reaction mixture was poured into methanol. The
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resulting precipitate was collected by filtration and purified through silica gel column
chromatography (n-hexane/dichloromethane = 1:1). DTD-CzDxz was obtained in a yield of
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980 mg (30%) as a bluish purple solid.
H NMR (500 MHz, CDCl3, δ, ppm): 8.43 (d, J = 7.6 Hz, 2H), 7.57 (d, J = 8.6 Hz, 2H), 7.32
(t, J = 6.4 Hz, 2H), 7.30 (d, J = 8.3 Hz, 2H), 7.17 (d, J = 8.4 Hz, 2H), 7.13 (d, J = 8.2 Hz, 2H),
4.04 (d, J = 6.6 Hz, 2H), 4.04 (d, J = 6.6 Hz, 2H), 2.04 (s, 2H), 1.22 (m, 80H), 0.88 (m, 12H).
Elemental analysis: anal. calcd for C78H110Cl2N4O2 (%): C, 77.64; H, 9.19; Cl, 5.88; N, 4.64;
O, 2.65. Found: C, 77.52; H, 9.16; N, 4.65. MALDI−TOF−MS (m/z): calcd for
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C78H110Cl2N4O2: 1206.64; found: 1206.81 [M]+
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2.3. Instrumentation
H-nuclear magnetic resonance (NMR) spectra of all compounds were recorded on a Bruker
500 MHz spectrometer using deuterated chloroform (Cambridge Isotope Laboratories, Inc.).
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Differential scanning calorimetry (DSC) measurements were conducted in nitrogen using a
TA Instruments Q2000 calorimeter. The samples were heated at a rate of 5 °C/min. The UV-
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Vis NIR absorption and photoluminescence (PL) spectra were obtained using an Agilent 8453
photodiode array UV-vis NIR absorption spectrometer and a Hitachi F-7000 fluorescence
spectrophotometer, respectively.
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2.4 Fabrication and characterization of thin films for halochromic sensors
The halochromic films were fabricated by coating DTD-CzDxz on a washed glass substrate.
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The glass substrate was cleaned by sonication for 10 min each in water, acetone, chloroform,
and isopropanol sequentially. As a sensing layer, 1% v/v DTD-CzDxz in CHCl3 solution was
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spin-coated at 2000 rpm for 40 s on the washed glass substrate. The bluish purple film
exposed to acid vapor changed to a colorless film, which returned to its original color very
quickly (<1.0 s) on exposure to air. Therefore, to observe the reversible acid sensing behavior
of the film, the film sample was placed in a quartz cuvette for exposure to acid vapor. The lid
was closed and the spectrum was recorded using UV-vis absorption spectroscopy.
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3. Result and discussion
3.1 Synthesis and physical properties
Compound 4 was synthesized by the condensation of 2,3,5,6-tetrachlorocyclohexa-2,5-diene-
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1,4-dione (chloranil) and 9-(2-decyltetradecyl)-9H-fluoren-3-amine through an electron
transfer reaction. DTD-CzDxz was finally synthesized in a 30% yield through a simple ringclosure reaction using potassium acetate and (diacetoxyiodo)benzene as the catalysts at room
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temperature.
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2
3
R=decyltetradecyl
DTD-CzDxz
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4
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Scheme 1. Synthetic route : (i) 2-decyltetradecyl bromide, NaH; (ii) HNO3, C2H4Cl2; (iii)
N2H4-H2O, Pd/C, KOAc, EtOH; (iv) chloranil, KOAc, EtOH; (v) (diacetoxyiodo)benzene,
KOAc, DMF/MeOH.
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Heat Flow (W/g)
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Heating cycle
Cooling cycle
Cooling
5
0
-5
Heating
-10
-15
150
200
250
300
o
Temperature( C)
Fig. 2. DSC curves of DTD-CzDxz during heating and cooling cycles.
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The chemical structure of DTD-CzDxz was characterized and confirmed by 1H-NMR,
Matrix assisted laser desorption ionization-time of flight, and elemental analysis. Because of
the poor solubility of common CzDxz-based pigments in organic solvents including
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dichloromethane, chloroform, and tetrahydrofuran, the long and bulky branched alkyl chains
were attached to the 9-position of each carbazole moiety to improve the solubility. The
thermal properties of DTD-CzDxz were investigated by DSC (Fig. 2). The reversible melting
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transition behavior of DTD-CzDxz was observed at 291 and 277 °C in the heating and
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cooling cycles, respectively, indicating moderately high thermal stability.
3.2 Optical and electrochemical properties
The absorption range of DTD-CzDxz in both solution and film states was measured by UVvis absorption spectroscopy. The DTD-CzDxz solution displayed highly intense absorption
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in the 400–700 nm wavelength region. The absorption spectrum of DTD-CzDxz in
chloroform showed λmaxabs at 615 nm (Fig. 3). The absorption spectra of DTD-CzDxz in
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different polar organic solvents were obtained and a small solvatochromic effect was
observed in dichloromethane (1.60 D) and tetrahydrofuran (1.75 D) (∆λmaxabs = 4 nm and 13
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nm, respectively).
The bandgap of a molecule changes according to the solvent polarity, thereby changing the
absorption region. The PL spectrum of DTD-CzDxz was also measured and showed a λmaxem
at 646 nm in chloroform solution. Moreover, a small solvatochromic effect was also observed
in dichloromethane and tetrahydrofuran (∆λmaxem = 2 nm and 15 nm, respectively). When HCl
[conc. = 1 × 10-2 M] was added to the DTD-CzDxz solution [conc. =1 × 10-5 M], the
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absorption wavelength range immediately shifted to show a prominent color change (Fig. 1).
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Fig. 3. (a) Absorption and PL spectra of DTD-CzDxz in CHCl3 solution. (b) Solvatochromic
behaviors; absorption and PL spectra of DTD-CzDxz in three different solvents.
When three different acids were added [conc. = 1 × 10-2 M] to the DTD-CzDxz solution,
the visible absorption bands in the range 450– 680 nm almost completely disappeared and
new absorption bands appeared in the NIR wavelength range (λ = 650–1000 nm). As shown
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in Fig. 4a, the absorption spectrum of the DTD-CzDxz in CHCl3 displayed red shift (∆λmaxabs.
= 256 nm) from the visible to NIR wavelength region after adding each acid.
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To clarify such a color change and unique performance, the halochromism of DTD-CzDxz
was investigated, as follows. The addition of acid to the DTD-CzDxz solution led to spectral
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transformation, which could be attributed to the protonation of the two nitrogens of oxazine.
Intramolecular charge transfer (ICT) absorption occurred because of the protonation of
nitrogen in the N-heteroaromatic electron accepting unit. Therefore, π-conjugated structures
with strong built-in donor–acceptor interactions tended to exhibit a more pronounced
halochromic effect owing to the enhanced ability of these structures to redistribute charge
density in the HOMO and LUMO levels and promote charge-transfer absorption in the NIR
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wavelength range.
NIR
region
0.4
0.2
0.0
300
0.6
0.4
0.2
0.0
400
500
600
700
800
900
400
1000
0.4
0.2
0.0
(d)
Absorbance (a.u.)
-3
HCl (4.68 x 10 M)
-3
HCl (5.85 x 10 M)
-3
HCl (7.02 x 10 M)
-3
HCl (8.19 x 10 M)
-3
HCl (9.36 x 10 M)
0.6
800
1000
DTD-CzDxz
-3
TFA (1.29 x 10 M)
-3
TFA (2.58 x 10 M)
-3
TFA (3.87 x 10 M)
-3
TFA (5.16 x 10 M)
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Absorbance (a.u.)
DTD-CzDxz
-3
HCl (1.17 x 10 M)
-3
HCl (2.34 x 10 M)
-3
HCl (3.51 x 10 M)
0.8
600
Wavelength (nm)
Wavelength (nm)
(c)
DTD-CzDxz
-3
H2SO4 (1.84 x 10 M)
-3
H2SO4 (3.68 x 10 M)
-3
H2SO4 (5.52 x 10 M)
-3
H2SO4 (7.32 x 10 M)
-3
H2SO4 (9.20 x 10 M)
-2
H2SO4 (1.10 x 10 M)
0.8
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0.6
(b)
Dxz
HCl
H2SO4
TFA
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Absorbance (a.u.)
0.8
Absorbance (a.u.)
(a)
0.8
-3
TFA (6.45 x 10 M)
-3
TFA (7.74 x 10 M)
-3
TFA (9.03 x 10 M)
-2
TFA (1.03 x 10 M)
0.6
0.4
0.2
0.0
600
800
1000
400
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Wavelength (nm)
600
800
1000
Wavelength (nm)
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Fig. 4. (a) UV-Vis absorption spectra of DTD-CzDxz solutions (1 × 10-5 M in CHCl3) with 1
× 10-2 M acid. UV-Vis absorption spectra of DTD-CzDxz solutions (1 × 10-5 M in CHCl3)
after adding (b) H2SO4, (c) HCl, and (d) TFA. (conc. of acid: 1 × 10-3 M – 1 × 10-2 M).
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Experimental conditions with incremental addition of acid (conc. of acid in DTD-CzDxz
solution= 1 × 10-3 M – 1 × 10-2 M) were applied, and the shifted absorption peak in the NIR
region gradually increased in intensity (Fig. 4b–d). As the concentration of acid in the
solution increased, the absorption intensity in the NIR wavelength range (λ = 650–1000 nm)
also increased, whereas that in the visible region (λ = 450–680 nm) decreased. This
phenomenon indicated the higher extent of quaternization and the occurrence of highly
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effective ICT. The phenomenon of the DTD-CzDxz (2H+) solution becoming transparent at
acidic conditions showed that protonation occurred only under diprotonation conditions (e.g.,
two-proton binding). As can be seen in Fig. 4, in comparison of the absorption spectra
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measured with varying the concentration of each acid, no spectral shift by mono-protonation
was observed and only the decrease of the absorbance in the same wavelength region was
displayed. Therefore, it can be conjectured that diprotonated DTD-CzDxz would be
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predominant in acidic conditions. Therefore, color change from bluish purple to colorless
transparent could be explained by the occurrence of simultaneous protonation on both sides
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of the nitrogen atom of the oxazine rings or negligibly fast sequential protonation after monoprotonation. [19, 31, 32] The PL spectral change of DTD-CzDxz solutions with the acid
concentration is displayed in Fig. S1 in the Supporting Information (SI).
and basic conditions
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3.3 Reversible absorption and fluorescence spectral behaviors of DTD-CzDxz under acidic
The reversible effect of protonation on the absorption and fluorescence of DTD-CzDxz is
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shown in Fig. 5. When TFA (conc. 5 × 10-3 M) was added to the DTD-CzDxz solution, the
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absorption intensity in the range 450–680 nm significantly weakened, and new absorption
bands appeared in the NIR region. As the concentration of the TFA solution increased, the
visible absorption band almost disappeared and the NIR absorption band intensities
strengthened remarkably. Subsequently, when TEA (conc. 6 × 10
-3
M) was added to the
DTD-CzDxz (2H+) solution formed above, the absorption spectrum was restored to the
original spectrum of initial DTD-CzDxz (Fig. 5a).
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Fig. 5. (a) UV/Vis absorption spectra and (b) PL spectra of DTD-CzDxz solutions (1 × 10-5
M in CHCl3) with addition of TFA and TEA. (c) Photographic images of DTD-CzDxz
solutions (1 × 10-5 M in CHCl3) with the concentration of TFA [① no TFA, ② 2.58 × 10-3 M,
-3
-3
-2
③ 5.16 × 10 M, ④ 7.74 × 10 M, ⑤ 1.03 × 10 M], and with the concentration of TEA.
[⑥ 2.16 × 10-3 M, ⑦ 3.60 × 10-3 M, ⑧ 5.04 × 10-3 M, ⑨ 6.48 × 10-3 M]
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Almost an identical reversible behavior could be observed in the PL spectra shown in Fig. 5b.
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The addition of TFA to the DTD-CzDxz solution quenched the emission at 650 nm. After the
addition of TEA to neutralize the above solution, the emission peak at 650 nm re-appeared
and the spectrum was found to be identical to that of original DTD-CzDxz. (Fig. S2)
Therefore, a reversible on/off switching behavior could be expected in the solution state by
adding acidic and basic species (Fig. 5c). The fluorescence images of DTD-CzDxz solution
before and after adding acid are shown in Fig. S3 in the SI
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Fig. 6. (a) UV-Vis absorption spectra of DTD-CzDxz thin film under exposure to HCl vapor.
(b) Absorbance at λmax (567 nm and 794 nm) vs. number of sensing cycles (i) under acid
vapor and (ii) in air.
As shown in Fig. 6a, the absorption spectra of the thin film displayed a similar red shift
(∆λmaxabs. = 227 nm) from the visible to NIR wavelength regions on exposure to acid vapors.
The thin film of DTD-CzDxz exhibited a highly reversible absorption spectral behavior,
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showing the color change from bluish purple to colorless in the presence of acid vapors.
Under ambient conditions without acid vapor, the color of the thin film was recovered
quickly from colorless to bluish purple. (Fig. S4) DTD-CzDxz, used as a thin film acid
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sensor, exhibited highly efficient cyclizability throughout the experiment. No significant
permanent degradation in the intensities and wavelengths of the absorption region was
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observed when the acid vapors were introduced into and removed from the sample more than
20 times under ambient conditions. The cyclizability measurements showed high efficiency
and stability in the sensing behavior of DTD-CzDxz and demonstrated that DTD-CzDxz can
be used as a solid-state devices showing very high sensitivity (Fig. 6b).
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4. Conclusion
A new halochromic compound, DTD-CzDxz, based on a fused nine-ring heteroaromatic
system was shown to exhibit unprecedentedly efficient halochromism with significant
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spectral shift of 256 nm (=∆λmaxabs) in the presence of acidic species. The shift in the
absorption spectra induced a color change from purple to colorless when the solutions or
films were exposed to acidic addition or acid vapors. Also, the optical properties of the DTD-
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CzDxz thin film were found to be useful for application as a pH sensor, showing fast
response to acid vapors owing to fast diprotonation. The bluish purple thin film of DTD-
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CzDxz became colorless and transparent when exposed to acid vapor, and therefore, the
DTD-CzDxz thin film could be considered as a good candidate for high-performance sensors
Acknowledgements
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for detecting acidic vapors in ambient environments.
This research was supported by the National Research Foundation of Korea
and
by
the
Key
Research
Institute
Program
EP
(NRF2015R1A2A1A05001876)
AC
C
(NRF20100020209).
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SUPPORTING INFORMATION
Highly Efficient Halochromic Behaviors in Solution and Film States
b]indolo[3,2-h]phenoxazine Derivative
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with 9,19-Dichloro-5,15-dihydrocarbazolo[3',4':5,6][1,4] oxazino[2,3-
Young Un Kim, Gi Eun Park, Suna Choi, Chang Geun Park, Min Ju Cho* and Dong
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Hoon Choi*
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Department of Chemistry, Research Institute for Natural Sciences, Korea University,
145 Anam-ro, Sungbuk-Gu, 02841 Seoul, Republic of Korea.
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Fig. S1. PL spectra of DTD-CzDxz solutions (1 × 10-5 M in CHCl3) after adding (a) H2SO4, (b)
HCl, and (c) TFA. (conc. of acid: 1 × 10-3 M–1 × 10-2 M). (d) PL spectra of DTD-CzDxz (1 × 10-5
M in CHCl3) after adding TEA (1 × 10-3 M – 6 × 10-3 M) sequentially to the solution bearing
TFA.
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Fig. S2. UV-Vis absorption spectra of DTD-CzDxz solutions (1 × 10-5 M in CHCl3) after adding
(a) TFA. (conc. of acid: 1 × 10-3 M – 1 × 10-2 M) and (b) TEA (1 × 10-3 M – 6 × 10-3 M). (c) Color
change observed in DTD-CzDxz solutions (1 × 10-5 M in CHCl3) with the concentration of TFA,
[① no TFA, ② 2.58 × 10-3 M, ③ 5.16 × 10-3 M, ④ 7.74 × 10-3 M, ⑤ 1.03 × 10-2 M] and
with the concentration of TEA. [⑥ 2.16 × 10-3 M, ⑦ 3.60 × 10-3 M, ⑧ 5.04 × 10-3 M, ⑨
5.76 × 10-3 M, and ⑩ 6.48 × 10-3 M]
Fig. S3. Fluorescence images taken before (a) and after (b) the addition of acid to the DTDCzDxz solution while irradiating 254 nm and 365 nm UV light.
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Fig. S4. Photographs of DTD-CzDxz film taken after exposure to (a) HCl vapor (0-0.4 s) and (b)
exposure to air. (c) Photographs obtained by repeatedly exposing the DTD-CzDxz film to acid
vapor and then to air. The number of repeated experiments is in parentheses.
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Highlight
- A new halochromic compound DTD-CzDxz bearing oxazine and phenoxazine was
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synthesized.
- The absorption spectrum shifted from the visible region to the near-infrared (NIR) region
for both solution and film states in acidic conditions.
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- When triethylamine was added into the acid-treated solution, the absorption spectrum was
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recovered to its initial one.
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