KR101545806B1 - Dye compound and method of preparing the dye compound - Google Patents
Dye compound and method of preparing the dye compound Download PDFInfo
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- KR101545806B1 KR101545806B1 KR1020140004516A KR20140004516A KR101545806B1 KR 101545806 B1 KR101545806 B1 KR 101545806B1 KR 1020140004516 A KR1020140004516 A KR 1020140004516A KR 20140004516 A KR20140004516 A KR 20140004516A KR 101545806 B1 KR101545806 B1 KR 101545806B1
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Abstract
The present invention relates to a triphenylamine-based dye compound having excellent optical activity and a process for producing the same.
Description
The present invention relates to a triphenylamine dye compound and a process for producing the dye compound.
Dye compounds are applied to various fields such as photovoltaic cells, solar cells, chemical sensors, and organic electroluminescent devices. As such a dye compound, a triazole-based compound, an oxadiazole-based compound, a pyrazoline-based compound, an arylamine-based compound, an oxazole-based compound, and an anthracene-based compound are widely known (see Patent Literature).
On the other hand, triphenylamine can not only be used as a strong electron donor in an initial state but also develops a dye compound containing the triphenylamine because of its ability to be stabilized in charge-transfer or excited state.
However, currently developed triphenylamine-based dyestuffs do not have sufficient optical activity, and thus a dye compound having excellent optical activity is required.
DISCLOSURE OF THE INVENTION An object of the present invention is to provide a novel dye compound having excellent optical activity in order to solve the above problems.
It is another object of the present invention to provide a process for producing the above-mentioned dye compound.
In order to accomplish the above object, the present invention provides a dye compound represented by the following formula (1).
[Chemical Formula 1]
The dye compound may have a maximum absorption wavelength range of 445 nm to 455 nm when analyzed by an ultraviolet-visible spectrophotometer in a polar solvent.
The present invention also provides a method for preparing the dye compound represented by Formula 1 by reacting a compound represented by
(2)
(3)
Since the dye compound of the present invention is combined with a stable and strong donor, triphenylamine, which is a good electron acceptor, coupled with a dioxane derivative, and has excellent optical activity, the dye compound of the present invention can be used for a photochemical or photoelectronic device such as a fluorescence sensor, laser, bipolar indicator, It can be usefully applied to applications.
Figure 1 shows the dye compound of the present invention analyzed by ultraviolet-visible light spectrophotometer.
2 and 3 are graphs showing v (cm -1 ) and fluorescence emission spectra of the dye compounds of the present invention.
4 shows the circulation current of the dye compound of the present invention.
5 shows the HOMO / LUMO energy state of the dye compound of the present invention.
Hereinafter, the present invention will be described.
The dye compound of the present invention is represented by the above formula (1), and the compound is named 5- [2- (4-diphenylamino-phenyl) -vinyl] -2,2-dimethyl- [1,3] dioxane- -Dione (5- [2- (4-diphenylamino-phenyl) -vinyl] -2,2-dimethyl- [1,3] dioxane-4,6-dione. The dye compound of the present invention is characterized by having a D-π-A (Donor-π-Accepter) structure as a dioxane derivative, which is an electron acceptor, is bonded to an electron donor triphenylamine. The D-π-A structure means a dipolar molecular structure having excellent charge separation. The dye compound of the present invention having such a molecular structure has excellent optical activity. Thus, the dye compounds of the present invention can be usefully applied in photochemical or optoelectronic applications.
Further, the compound of the present invention is excellent in solubility in a polar solvent because it is easy to interact with a polar solvent by a ketone and a methyl group contained in the dioxane derivative.
Such a dye compound of the present invention can exhibit a maximum absorption wavelength range of 445 nm to 455 nm (specifically about 450 nm) upon analysis with a UV / Vis spectrophotometer in a polar solvent.
The method for preparing the dye compound of the present invention is not particularly limited, but may be produced by reacting a compound represented by the following formula (2) with a compound represented by the following formula (3).
(2)
(3)
Specifically, the compound represented by
Hereinafter, the present invention will be described in detail with reference to examples. However, these examples are for illustrating the present invention specifically, and the scope of the present invention is not limited to these examples.
[Example 1] Dye compound synthesis
0.55 g (2 mmol) of 3-formyltriphenylamine and 0.29 g (2 mmol) of 2,2-dimethyl- [1,3] dioxane-4,6-dione were added to ethanol and refluxed for 1 hour. Then, distilled water was poured into the reaction solution to obtain a red precipitate, which was filtered. The filtered precipitate was washed with ethanol and then dried to obtain the dye compound (5- [2- (4-diphenylamino-phenyl) -vinyl] -2,2-dimethyl- [1,3] dioxane- ) Were synthesized. 1 H NMR and MS data of the synthesized dye compound are as follows (analyzed by NMR spectrometer (JEOL-AL400) operating at 400 Hz).
1 H NMR (400 MHz, DMSO -d 6) δ 1.78 (s, 6 H), δ 6.93 (d, 2H), δ 7.22 (m, 8H), δ 8.11 (d, 2H), δ 8.29 (s, 1H)
MS m / z: 399 (M < + >).
[Experimental Example 1] Absorption spectrum analysis
The dye compound synthesized in Example 1 was added to various solvents to analyze the absorption spectrum, and the results are shown in Fig. The spectrophotometer used was a UV / Vis spectrophotometer (Agilent 8453) and a dye compound of 1 × 10 -5 M was used.
Referring to FIG. 1, it can be seen that the maximum absorption peak appears at about 450 nm. As the polarity of the solvent increases, the psychochromatic effect (effect of shifting the maximum wavelength of the absorption spectrum of the substance toward the long wavelength side .
This maximum absorption peak (υ max ) was studied by the Kamlet-Taft parameter.
The Kamlet-Taft parameter represents the linear salvation energy participation between the solute and the solvent according to Equation (1) below.
[Equation 1]
In Equation (1), a, b, and delta are constants of a solute unaffected by a solvent,? Is a hydrogen bonding donor ability, and? Is a hydrogen accepting ability. Also, π * is a bipolar polarizable property associated with a given solvent, and δ is a corrected polarization ratio belonging to the shape of the solvent. υ max (solute) is the value measured by the UV / Vis absorption band energy, and υ max , 0 is the UV / Vis absorption band energy reference value.
&Quot; (2) "
Based on these points, the Kamlet-Taft parameter for various solvents, Reichardt '
Referring to Table 1, it can be confirmed that the dye compound of the present invention is excellent in solubility by the opened ketone and methyl group of the dioxane derivative. Further, the maximum absorption peak
Referring to FIG. 2, which shows the measured experimental υ (cm -1 ) plot
Referring to FIG. 3, which also shows the fluorescence emission spectrum (analyzed by Shimadzu RF-5301PC spectrophotometer) of the dye compound of the present invention
[Experimental Example 2] HOMO / LUMO band energy gap
The HOMO / LUMO band energy gap was confirmed by applying a cyclic voltammogram. The cyclic voltammogram consisted of three electrodes including the reference Ag / Ag +, the glassy carbon in operation and the platinum wire of the counter electrode. The oxidation and reduction onset potential points in an acetonitrile solution containing tetrabutylammonium hexafluorophosphate, which is an electrolytic solution, are as shown in FIG.
HOMO and LUMO were calculated by the oxidation-reduction onset potential point shown in FIG. 4 and the following equation (3).
&Quot; (3) "
In Equation 3, E peakonset is the onset potential in the dye compound and E 1/2 ( ferrocene ) is the half-wave potential (0.42 eV) of the ferrocene. On the other hand, the HOMO was 0.753 eV and the LUMO was -0.895 eV. As a result of applying these values, HOMO was -5.133 eV and LUMO was -3.521 eV.
The computed HOMO and LUMO values were computed to simulate the energy density states of the dye compounds and the results are shown in FIG. Referring to FIG. 5, it can be seen that the conversion of HOMO to LUMO in the D-π-A structure of the dye compound is accompanied by an excellent absorption band in the visible region. In addition, it can be seen that the non-electron pairs in triphenylamine and dioxane derivatives are affected by the other bipolarity of the solvent. On the other hand, the electron transfer between HOMO and LUMO
Claims (3)
[Chemical Formula 1]
Dye compounds with a maximum absorption wavelength range of 445 nm to 455 nm when analyzed by a UV / Vis spectrophotometer in polar solvents.
(2)
(3)
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101047976B1 (en) * | 2008-10-15 | 2011-07-13 | 경북대학교 산학협력단 | New Solvatochromic Dyes |
| KR101157743B1 (en) * | 2010-05-03 | 2012-06-25 | 경북대학교 산학협력단 | Dye for dye-sensitized solar cell and solar cell including the same |
| KR101163032B1 (en) * | 2009-11-23 | 2012-07-09 | 충남대학교산학협력단 | Triphenylamin derivative electro luminescent dye and its preparation method |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101047976B1 (en) * | 2008-10-15 | 2011-07-13 | 경북대학교 산학협력단 | New Solvatochromic Dyes |
| KR101163032B1 (en) * | 2009-11-23 | 2012-07-09 | 충남대학교산학협력단 | Triphenylamin derivative electro luminescent dye and its preparation method |
| KR101157743B1 (en) * | 2010-05-03 | 2012-06-25 | 경북대학교 산학협력단 | Dye for dye-sensitized solar cell and solar cell including the same |
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