JP2011093841A - Anthracene derivative and pyrene derivative - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coloring matter for organic laser, having excellent durability against light irradiation and emitting light in high efficiency. <P>SOLUTION: There is provided a fluorescent coloring matter exhibiting high stability (against oxidation reaction, radical reaction, photoreaction or the like) and highly efficient light emission (high absorbance and high quantum efficiency), and capable of being dispersed in a polymer or a liquid crystal solvent in high concentration. Concretely, there is provided the compound obtained by introducing aryl groups to easily oxidizable four points of pyrene and two points of anthracene, and further introducing dissolvable long-chain alkyl groups to the aryl groups. These coloring matters especially are aimed at organic lasers oscillating at low thresholds and continuous oscillation thereof. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to anthracene or pyrene derivatives having suitable properties. The anthracene derivative of the present invention can be particularly preferably used as a dye for an organic laser.

  Many organic dyes for lasers have been developed so far (see Non-Patent Documents 1 to 5), but most of them are for liquid lasers and very few dyes for solid-state lasers. In addition, there were very few dyes satisfying both high stability and high efficiency light emission. Therefore, new dyes are required in the development of cholesteric liquid crystal lasers.

  For example, a conventional dye represented by the following formula (referred to as “DCM”) has a defect of being readily decomposed by a YAG laser or the like, although it has an excellent luminous ability.

V. de Halleux et al., Adv. Funct. Mater., 14, no. 7, pages 649-659 T. M. Figueira-Duarte et al., Angew. Chem., 2008, 120, pages 10329-10332. M. Ozaki et al., Adv. Mater. 4, pages 307-309 J. Schmidtke et al., Adv. Mater., 2002, 14, No. 10, pp. 746-749 M. H. Song et al., Adv. Mater., 2004, 16, No. 9-10, 779-783

  The objective of this invention is providing the organic compound which can eliminate the fault of the above-mentioned prior art.

  An object of the present invention is to provide an organic laser dye that is excellent in durability against light irradiation and emits light with high efficiency. The term “durability against light irradiation” as used herein means that a molecular structure such as a molecular bond is not changed even when light irradiation or repeated light irradiation is performed for a long time. Specifically, the evaluation is based on the fact that the NMR of the compound does not change and the fluorescence intensity of the compound does not change with respect to the time or number of times the compound is irradiated with light having an absorption wavelength.

  As a result of intensive studies, the present inventor has found that a compound having a specific basic skeleton (that is, anthracene and / or pyrene skeleton) and having an aryl group at a specific position is excellent in durability when high energy is applied. It was. For example, it is known that the bromination or oxidation reaction of pyrene occurs specifically at the 1, 3, 6 and 8 positions, and unlike benzene and naphthalene, the reaction proceeds easily without catalyst (H. Maeda et al., Eur J. Chem., 2006, 12, 824). Therefore, when an aryl group such as a phenyl group or a naphthyl group which is not easily oxidized is introduced at the corresponding position, the stability is greatly improved. As a result of further research based on the above findings, the present inventors have also found that these compounds have high luminous efficiency at a suitable wavelength.

The anthracene derivative of the present invention is based on the above findings, and more specifically is an anthracene derivative having an aryl group at the 9th and 10th positions represented by the general formula (1) described later (in the formula (1), Ar Is any aryl group selected from the group consisting of the general formulas (2) to (14) described later; Ar ¹ and Ar ² may be the same or a part of them may be different.

According to the present invention, a pyrene derivative having a 1, 3, 6, 8-aryl group represented by the general formula (15) described later (in the formula (2), Ar ^{1 to} Ar ⁴ are the following Any aryl group selected from the group consisting of the general formulas (2) to (14); the Ar ^{1 to} Ar ⁴ may be the same or a part of them may be different.

  As described above, according to the present invention, an organic compound capable of exhibiting good characteristics is provided.

  The anthracene or pyrene derivative of the present invention can exhibit the following effects, for example.

(1) A new high-stability and high-efficiency luminescent dye directed to a laser dye can be realized.

(2) High stability is obtained as a laser dye. For example, high durability can be exhibited particularly under laser irradiation conditions such as heat, oxidation reaction and radical reaction.

(3) Highly efficient light emission can be obtained as a laser dye. For example, it is possible to obtain high light emission efficiency such that the molar absorption coefficient (ε) at the laser irradiation wavelength is 10,000 L · M ⁻¹ · cm ⁻¹ or more and the fluorescence quantum yield (Φ) is 0.8 or more.

(4) High compatibility with a solvent is obtained as a laser dye. For example, a design capable of exhibiting high compatibility with a liquid crystal phase is easy. If the compatibility with the liquid crystal is high, the molecules are easily oriented in a state of being dissolved in the liquid crystal phase, and coherent fluorescence, which is a laser oscillation condition, is easily obtained. As for the compatibility with the liquid crystal phase, it is transparent and uniform when observed visually or with a microscope having a magnification of about 10 times. More specifically, the UV-visible absorption spectrum overlaps the absorption spectrum of the compound and the liquid crystal compound. It can be confirmed by the combination.

2 is a chart showing ¹ H-NMR data obtained in Example 1. FIG. 2 is a chart showing ¹ H-NMR data obtained in Example 1. FIG. 2 is a chart showing UV-Vis absorbance data obtained in Example 1. FIG.

2 is a chart showing ¹ H-NMR data obtained in Example 2. FIG. 2 is a chart showing ¹ H-NMR data obtained in Example 2. FIG. 2 is a chart showing ¹ H-NMR data obtained in Example 2. FIG.

2 is a chart showing UV-Vis absorbance data obtained in Example 2. FIG. 2 is a chart showing ¹ H-NMR data obtained in Example 3. FIG. 6 is a chart showing UV-Vis absorbance data obtained in Example 3.

2 is a chart showing ¹ H-NMR data obtained in Example 4. FIG. 6 is a chart showing ¹³ C-NMR data obtained in Example 4. FIG. 6 is a chart showing UV-Vis absorbance data obtained in Example 4.

  Hereinafter, the present invention will be described more specifically with reference to the drawings as necessary. In the following description, “parts” and “%” representing the quantity ratio are based on mass unless otherwise specified.

(Anthracene derivative)
The “anthracene derivative” according to the first aspect of the present invention is an anthracene derivative having an aryl group at the 9th and 10th positions represented by the following general formula (1).

(Aryl group)
In the above formula, Ar ¹ and Ar ² are groups represented by any one of the following general formulas (2) to (14). These Ar ¹ and Ar ² may all be the same or may be partially or completely different. From the viewpoint of simplicity in producing the anthracene derivative of the present invention, it is preferable that Ar ¹ and Ar ² are the same.

(Pyrene derivatives)
The “pyrene derivative” according to the second aspect of the present invention is a pyrene derivative having a 1, 3, 6, 8-aryl group represented by the following general formula (15).

（式中、Ａｒ^１〜Ａｒ^４は、下記一般式（２）〜（１４）からなる群から選ばれるいずれかのアリール基であり；該Ａｒ^１〜Ａｒ^４は全て同じでも、それらの一部が異なっていてもよい）。

(Wherein Ar ^{1 to} Ar ⁴ are any aryl groups selected from the group consisting of the following general formulas (2) to (14); Ar ^{1 to} Ar ⁴ may all be the same or a part thereof) May be different).

（一般式（２）〜（１４）中、Ｒ^１〜Ｒ^３は、炭素数１〜１８の直鎖または分岐状のアルキル基、ベンジル基またはフェニル基およびそれらの炭化水素置換基を有する誘導体、アルキルエーテル基、アルキルエステル基、芳香族エステル基、アルキレンエーテル基、水素。更に、フッ化アルキル官能基を含むアルキル基、アルキルエーテル基、アルキルエステル基、芳香族エステル基、アルキレンエーテル基である；該Ｒ^１〜Ｒ^３は、全てが同じでも、一部が異なっていてもよい）。

(In General Formulas (2) to (14), R ^{1 to} R ³ are each a linear or branched alkyl group having 1 to 18 carbon atoms, a benzyl group or a phenyl group, and a derivative having a hydrocarbon substituent thereof, An alkyl ether group, an alkyl ester group, an aromatic ester group, an alkylene ether group, hydrogen, and an alkyl group containing a fluorinated alkyl functional group, an alkyl ether group, an alkyl ester group, an aromatic ester group, an alkylene ether group; R ^{1 to} R ³ may be all the same or partially different.

(Suitable aryl group)
From the standpoint of high quantum efficiency as a laser dye, Ar is a biphenyl skeleton (general formulas 2 and 4), a terphenyl skeleton (general formulas 3 and 5), a naphthyl skeleton (general formulas 6 to 8), anthracene. A skeleton (general formulas 9 to 11) is preferable.

  Furthermore, Ar has a biphenyl skeleton (general formulas 2 and 4), a terphenyl skeleton (general formulas 3 and 5), and a naphthyl skeleton (general formulas 6 to 8) from the viewpoint of simplicity of the manufacturing method and solubility. It is particularly preferred.

(Preferred substituent)
R in general formula (2) to general formula (14) (R ^{1 to} R ³ are each a straight chain or branched alkyl group having 1 to 18 carbon atoms, a benzyl group or a phenyl group, and hydrocarbon substitution thereof. Group-containing derivatives, alkyl ether groups, alkyl ester groups, aromatic ester groups, alkylene ether groups, hydrogen. Further, an alkyl group containing a fluorinated alkyl functional group, an alkyl ether group, an alkyl ester group, an aromatic ester group, and an alkylene ether group. R ^{1 to} R ³ may all be the same or different.

(Particularly preferred substituents)
Although not particularly limited, the following conditions are suitable because it is highly preferable to impart high solubility in organic solvents, dispersion in polymer solvents, and adsorption ability to various surfaces to the dye.

  R is preferably a linear or branched alkyl group having 1 to 18 carbon atoms, an alkyl ether group, an alkylene ether group, or hydrogen because of its high solubility. Furthermore, an alkyl group containing a fluorinated alkyl functional group and an alkyl ether group.

  Furthermore, in view of the availability of raw materials, particularly preferred are linear or branched alkyl groups having 1 to 12 carbon atoms, alkyl ether groups, polyoxyethylene groups, alkyl groups and alkyl ether groups containing fluorinated alkyl functional groups. It is.

Moreover, about the kind of R < ¹ > -R < ³ >, from the simplicity of a manufacturing method, Preferably R < ¹ > -R < ³ > is the same component. Or when comprised by a different component, it is preferable that at least one is a methyl group, a methoxy group, or hydrogen.

(Compound with high luminous efficiency)
The “luminescence efficiency” of fluorescence obtained by irradiating a certain substance with light is defined by the ratio of the incident light amount (I ₀ ) and the emitted light amount (I _F ), and the absorbed light amount (I ₀ · (1− T)) and the amount of luminescence (I _F ), which is a function of the fluorescence quantum yield (Φ). That is,
“Luminescence efficiency” = I _F / I ₀ = Φ · (I ₀ · (1-T)) / I ₀ = Φ · (1-T)
It is. Here, T is a transmittance defined by a ratio I / I ₀ of the amount of light (I ₀ ) irradiated to the substance and the amount of light (I) transmitted through the substance, and the molar extinction coefficient (ε [L -M ^{< -1} > cm ^<-1 >]) is so small that it is large. The absorbance (denoted as A) defined by the common logarithm log (T ⁻¹ ) of the reciprocal of T is a range where the compound concentration is low (depending on the compound, for example, T> 0.95, A <0.02) In the concentration range), Lambert-Beer's law of the following formula is established.
A = log (T ⁻¹ ) = ε · c · d (c is the concentration [M · L ⁻¹ ], d is the optical path length [cm])

Therefore, at a low concentration of the compound, “luminescence efficiency” is represented by the following formula.
"Luminous efficiency" ^{= Φ × (1-10 - (-} ε · c · d))
From the above equation, it is obvious that “luminescence efficiency” increases as ε increases and Φ increases within the range in which Lambert-Beer's law is established. When the compound concentration is high, there is total absorption of irradiation light and reabsorption of fluorescence, which deviates from the above equation, but the point is that the “emission efficiency” increases as ε increases and Φ increases. There is no. Therefore, a compound having a large ε and a large Φ can be referred to as a compound having a high “luminescence efficiency”. Whether or not a compound oscillates can be caused by factors other than “luminescence efficiency”, but the large “luminescence efficiency” is an indispensable factor for laser oscillation.

(Method for producing anthracene / pyrene derivative)
Although the manufacturing method of the pigment | dye as described in the said General formula (1) and (2) is not specifically limited, As shown in an Example, it respond | corresponds with 9,10- dibromoanthracene and 1,3,6,8-tetrabromopyrene. There is a method (Suzuki-Miyaura method) in which a boronic acid or boronic acid ester of an aryl group is cross-coupled using a palladium (O) or (II) catalyst.

  In addition, magnesium derivatives (Kumada-Tamao method), tin derivatives (Stille method), silicon derivatives (Hiyama method), zinc derivatives (Yamamoto method), etc. can be used as transmetallation agents for aryl groups. Nickel complexes (Kumada-Tamao method and Yamamoto method) and palladium complexes (Stille method and Hiyama method) can be used as the catalyst. In addition, a method of forming a biaryl bond by a cross coupling method can be applied.

  In the dyes described in the general formulas (1) and (2), an aryl group is introduced at the most reactive position of anthracene and pyrene, and the decomposition reaction of polycyclic aromatic compounds including oxidation reaction Is less likely to occur.

(Preferred embodiment-1: fluorescence behavior of anthracene derivative represented by general formula (1))
The anthracene derivative represented by the general formula (1) exhibits a large molar extinction coefficient (ε [L · M ⁻¹ · cm ⁻¹ ]) in the region of 300 to 450 nm, and a large emission quantum yield (Φ) in the blue region. ).

(Molar extinction coefficient)
In the irradiation light wavelength 300nm or more areas, chloroform, THF, maximum molar extinction coefficient in an organic solvent such as toluene ^{(ε [L · M -1 ·} cm -1]) is, 3000L ^· M ^{-1 · cm} -1 Or more, preferably 6000 L · M ⁻¹ · cm ⁻¹ or more, particularly preferably 10000 L · M ⁻¹ · cm ⁻¹ or more.

The molar extinction coefficient (ε [L · M ⁻¹ · cm ⁻¹ ]) can be measured using the following measurement method.

(Measurement method of molar extinction coefficient)
The molar extinction coefficient (ε [L · M ⁻¹ · cm ⁻¹ ]) is measured by the following method. Using a UV-Vis spectrophotometer (UV-Vis), the absorbance (A) at an arbitrary wavelength of a solution obtained by dissolving the dye compound in a measurement solvent is measured. At this time, Lambert-Beer's law A = ε · c · d (c is the concentration [M · L ⁻¹ ], d is the optical path length [cm])
Is used, ie, a solution adjusted to a concentration where A at the maximum wavelength of the absorption spectrum is 0.02 or less.
From the above equation, ε = A / (c · d) [L · M ⁻¹ · cm ⁻¹ ] can be obtained.

(Fluorescence quantum efficiency)
The fluorescence quantum efficiency is 0.50 or more in an organic solvent such as chloroform, THF or toluene (concentration: 1.0 × 10 ⁻⁵ M · l ⁻¹ or less), preferably 0.60, particularly preferably 0.8. 70.

  Said fluorescence quantum efficiency can be measured using the following measuring system.

  The luminescence quantum yield (Φ) was obtained by dissolving the dye compound in a measurement solvent so that the absorbance at an arbitrary wavelength was 0.1, and an absolute quantum yield measurement device C9920-02 manufactured by Hamamatsu Photonics Co., Ltd. It measured using. This method is widely used and is also described in, for example, Japanese Patent Application Laid-Open No. 2008-56630.

(Preferred embodiment-2: fluorescence behavior of pyrene derivative represented by general formula (15))
The pyrene derivative represented by the general formula (15) is characterized by exhibiting a large molar extinction coefficient (ε) in the region of 300 to 450 nm and a large emission quantum yield (Φ) in the blue region.

(Molar extinction coefficient)
In the irradiation light wavelength 300nm or more areas, chloroform, THF, maximum molar extinction coefficient in an organic solvent such as toluene ^{(ε [L · M -1 ·} cm -1]) is, 3000L ^· M ^{-1 · cm} -1 Or more, preferably 10,000 L · M ⁻¹ · cm ⁻¹ or more, and particularly preferably 15000 L · M ⁻¹ · cm ⁻¹ or more.

The fluorescence quantum efficiency is 0.70 or more, preferably 0.80 or more, particularly preferably 0 in an organic solvent such as chloroform, THF, and toluene (concentration: 1.0 × 10 ⁻⁵ M · l ⁻¹ or less). .90 or more.

The molar extinction coefficient (ε [L · M ⁻¹ · cm ⁻¹ ]) and luminescence quantum yield (Φ) of the above pyrene derivative can be measured by the same method as those of the above-described anthracene derivatives.

  Hereinafter, the present invention will be described more specifically with reference to examples.

<Experimental equipment used>
¹ H NMR and ¹³ C NMR spectra were measured using TNM as a reference substance using LNM-EX400 manufactured by JEOL.

  The infrared spectrum (IR) was measured using JASCO Corporation FT-IR460 pulses spectrometer, the ultraviolet visible spectrum was measured using Beckman DU700, the fluorescence spectrum was measured using JASCO FP-6500, and the fluorescence lifetime was measured using Hamamatsu Photonics OB920.

  Mass spectrometry (HRMS) was measured by FAB-MASS using JMS-700 manufactured by JEOL Ltd.

  Recycle preparative HPLC was performed using a UV-310 detector, RI-50S detector, and JAIGEL-1H-A column manufactured by JAI, using chloroform as a developing solvent.

Example 1
(Compound A)
The synthesis scheme used in this example is shown in the following formula (16).

4'-heptylbiphenyl-4-ylboronic acid (A-1)
To a THF (20 ml) solution of 4-bromo-4′-heptylbiphenyl (1.65 g, 5 mmol) was added dropwise a 2.6 m hexane solution (1.2 equivalents) of butyllithium at −78 ° C. in an argon atmosphere. The mixed solution was stirred at −78 ° C. for 1 hour, trimethyl borate (1.4 equivalents) was added dropwise, and the mixture was further stirred at room temperature for one day. Thereafter, a 2 basis aqueous HCl solution was added and the mixture was further stirred for 18 hours. After stopping the reaction, extraction with CH ₂ Cl ₂ was performed by a liquid separation operation, washing was performed with water, and the obtained organic solvent was dried with MgSO ₄ and then the solvent was removed by distillation under reduced pressure. The obtained solid was recrystallized using a mixed solution of hexane and chloroform to obtain the target compound (0.96 g, 65%).

¹ H NMR (400 mHz, DMSO): δ 7.83 (d, J = 6.64, Ar—H, 2H), 7.58 (t, J− = 6.7, Ar—H, 4H), 7 .26 (d, J = 7.0, Ar—H, 2H), 0.84 (t, J = 5.4, —CH ₃ , 3H)

9, 10-bis (4'-heptyl-1--4-biphenyl) anthracene (A)

A 1M Na ₂ CO ₃ aqueous solution (1 ml), toluene (10 ml), and THF (10 ml) sufficiently bubbled with argon were added to 4′-heptylbiphenyl-4-ylboronic acid (0.29 g, 1 mmol), dibromoanthracene (0 ml) under an argon atmosphere. .17 g, 0.5 mmol) and Pd (PPh ₃ ) ₄ (0.05 equivalent), and the mixture was stirred at 110 ° C. for 3 days. After stopping the reaction, extraction with CH ₂ Cl ₂ was performed by a liquid separation operation, washing was performed with water, and the obtained organic solvent was dried with MgSO ₄ and then the solvent was removed by distillation under reduced pressure. The catalyst was removed using a silica gel column packed with a mixed solvent of hexane and chloroform, and then the target compound was fractionated using HPLC, and recrystallized using hexane to obtain the target compound (20 mg 6%).

¹ H NMR (400 mHz, CDCl ₃ ): δ 7.29-7.85 (m, Ar—H, 8H), 7.70 (d, J− = 7.8, Ar—H, 4H), 7. 55 (d, J = 7.8, Ar—H, 4H), 7.3-7.38 (m, Ar—H, 8H), 0.91 (t, J = 6.3, —CH ₃ , 6H) FT-IR

HRMS (FAB) Calcd for C ₅₂ H ₅₄ : 678.4226,
Found: 678.4217

The ¹ H NMR charts obtained here are shown in FIGS.

  The optical properties obtained here are shown in Table 1 and FIG.

Example 2 (Compound B)
The scheme of the synthesis method is shown in the following formula (17).

2-bromo-6-hexyloxynaphtalene (B-1)

Acetonitrile (30 ml) was added to 6-bromo-2-naphthol (1.8 g 8.0 mmol), K ₂ CO ₃ (1.38 g, 10.0 mmol), and bromohexane (1.24 g, 7.5 mmol) to obtain a mixed solution. Refluxed for 18 hours. After stopping the reaction, extraction with CH ₂ Cl ₂ was performed by a liquid separation operation, washing was performed with water, and the obtained organic solvent was dried with MgSO ₄ and then the solvent was removed by distillation under reduced pressure. The target compound was obtained by recrystallizing the obtained solid using hexane. (2.63 g, 99%)

¹ H NMR (400 mHz, CDCl ₃ ): δ 8.60 (d, J = 8.8, Ar—H, 2H), 7.71 (d, J− = 9.0, Ar—H, 2H), 7.57-7.60 (m, Ar-H, 2H), 7.36-7.39 (m, Ar-H, 2H), 7.30 (d, J = 8.3, Ar-H, 2H), 7.11 (d, J = 8.5 Ar—H, 2H), 4.10 (t, J = 6.6, Ar—O—CH ₂ , 2H), 0.95 (t, J _{- = 7.8, -CH 3, 3H} )

(Compound B-2)
6-hexyloxynapthtyl-2-bronic acid (B-2)

The target compound was obtained by the same operation as in the boronic acid synthesis method of Compound A-1 (0.50 g, 37%). The reagent used was 2-bromo-6-hexyloxynaphthalene (1.54 g, 5 mmol) in THF (20 ml) n-BuLi and B (OMe ₃ ).

(Compound B)
9, 10-bis (6-hexlyoxy-2-naphtyl) anthracene (B)

The target compound was obtained by the same operation as Suzuki coupling of Compound A-2 (50 mg, 16%). The reagents used were dibromoanthracene (0.17 g, 0.5 mmol), 6-hexyloxynapthtyl-2-bronic acid (0.27 g, 1 mmol), Pd (PPh ₃ ) ₄ in 1M Na ₂ CO ₃ (1 ml), toluene ( 20ml)

¹ H NMR (400 mHz, CDCl ₃ ): δ 7.95 (d, J = 8.3, Ar—H, 2H), 7.9 (s, Ar—H, 2H), 7.81 (d, J = 8.9.2 Ar-H, 2H), 7.73-7.76 (m, Ar-H, 4H), 7.55-7.58 (m, Ar-H, 2H), 7.26. −7.32 (m, Ar—H, 8H), 4.18 (t, J = 6.6, Ar—O—CH ₂ , 4H), 0.95 (t, J− = 7.3, − CH _3, 6H)

_{HRM (EI) Calcd for C 46} H 46 O 2: 630.3498,
Found: 630.3491

The ¹ H NMR chart obtained above is shown in FIGS.

  The optical properties obtained above are shown in FIG. 7 and Table 2 below.

Example 3 (Compound C)

The scheme of the synthesis method is shown in the following formula (17).

1, 3, 6, 8-tetrabromopyrene

  Bromination of the 1, 3, 6, and 8 positions of pyrene was performed according to the following (Document A).

(Document A): S. Bernhardt, M. Kastler, V. Enkelmann, M. Baumgarten, K. Muellen, Chem. Eur. , 2006, 12, 6117-6128

  Pyrene (1 g, 4.9 mmol) was dissolved in nitrobenzene (30 ml) and bromine (1 ml, 20.3 mmol) was added dropwise in an argon atmosphere. After completion of the dropwise addition, the reaction temperature was raised to 160 ° C. and stirred for 3 hours. After cooling the reaction solution to room temperature to stop the reaction, the reaction solution was poured into acetone, and a precipitate was obtained by suction filtration. Since the obtained precipitate was insoluble in a general organic solvent, it was used as it was without purification.

(Compound C-1)
1,3,6,8-tetrakis (4'-n-heptyl-4-biphenyl) pyrene (C)

The target compound was obtained by the same operation as Suzuki coupling of Compound A-2 (30 mg, 10%). The reagents used were 1,3,6,8-tetrabromopyrene (0.13 g, 0.25 mmol), 4′-heptylbiphenyl-4-ylboronic acid (0.29 g, 1 mmol), Pd (PPh ₃ ) ₄ in 1M Na. ₂ CO ₃ (5 ml), toluene (30 ml)

¹ H NMR (400 mHz, CDCl ₃ ): δ 8.30 (s, Ar—H, 4H), 8.12 (s, Ar—H, 2H), 7.77 (s, Ar—H, 16H), 7.64 (d, Ar-H, 8H), 7.31 (d, Ar-H, 8H), 0.90 (t, J = 6.8, -CH 3, 12H) HRMS (FAB) Calcd for _{C 92 H 98: 1202.7669, Found} : 1202.7628

The ¹ H NMR chart obtained above is shown in FIG.

  The optical properties obtained above are shown in FIG. 9 and Table 3 below.

Example 4 (Compound D)

The synthesis method scheme is shown in the following formula (19).

1,3,6,8-tetrakis (6-n-hexyloxy-2-naphtyl) pyrene (D)

The target compound was obtained by the same operation as Suzuki coupling of Compound 2 (30 mg, 11%). The used reagents were 1,3,6,8-tetrabromopyrene (0.13 g, 0.25 mmol), 6-hexyloxynapthtyl-2-bronic acid (0.27 g, 1 mmol), Pd (PPh ₃ ) ₄ in 1M Na _2. CO ₃ (5 ml), toluene (30 ml)

¹ H NMR (400 mHz, CDCl ₃ ): δ 8.26 (s, Ar—H, 4H), 8.20 (s, Ar—H, 2H), 8.08 (s, Ar—H, 4H), 7.79-7.90 (m, Ar-H, 12H), 7.20-7.28 (m, Ar-H, 4H), 4.13 (t, J = 6.6, O-CH 2 −4H), 0.93 (t, J = 6.6, —CH ₃ , 6H) ppm, ¹³ C NMR (100 mHz, CDCl ₃ ): δ 141.60, 141.37, 137.39, 136. 35, 133.86, 129.57, 129.38, 129.26, 128.99, 126.62, 119.55, 106.71, 103.65, 68.22, 31.64, 29.28, 25.82, 22.61, 14.00 ppm

FIG. 10 shows the ¹ H-NMR chart obtained above, and FIG. 11 shows the ¹³ C-NMR chart.

_{HRMS (FAB) Calcd for C 80} H 82 O 4: 1106.6213,
Found: 1106.6213

  The optical properties obtained above are shown in FIG. 12 and Table 4 below.

Claims (8)

An anthracene derivative having an aryl group at positions 9 and 10 represented by the following general formula (1).

(In the formula, Ar is any aryl group selected from the group consisting of the general formulas (2) to (14); Ar ¹ and Ar ² may be the same or a part of them may be different) Good).

(In General Formulas (2) to (14), R ^{1 to} R ³ are each a linear or branched alkyl group having 1 to 18 carbon atoms, a benzyl group or a phenyl group, and a derivative having a hydrocarbon substituent thereof, An alkyl ether group, an alkyl ester group, an aromatic ester group, an alkylene ether group, hydrogen, and an alkyl group containing a fluorinated alkyl functional group, an alkyl ether group, an alkyl ester group, an aromatic ester group, an alkylene ether group; R ^{1 to} R ³ may be all the same or partially different. A pyrene derivative having a 1, 3, 6, 8-aryl group represented by the following general formula (15).

(Wherein Ar ^{1 to} Ar ⁴ are any aryl groups selected from the group consisting of the following general formulas (2) to (14); Ar ^{1 to} Ar ⁴ may all be the same or a part thereof) May be different).

(In General Formulas (2) to (14), R ^{1 to} R ³ are each a linear or branched alkyl group having 1 to 18 carbon atoms, a benzyl group or a phenyl group, and a derivative having a hydrocarbon substituent thereof, An alkyl ether group, an alkyl ester group, an aromatic ester group, an alkylene ether group, hydrogen, and an alkyl group containing a fluorinated alkyl functional group, an alkyl ether group, an alkyl ester group, an aromatic ester group, an alkylene ether group; R ^{1 to} R ³ may be all the same or partially different. A method of generating fluorescence by irradiating a complex comprising at least the anthracene derivative according to claim 1 and a matrix with excitation light including a wavelength band of 300 to 450 nm;
Luminescence with a fluorescence quantum yield (Φ) of 0.8 or more using a wavelength at which the molar extinction coefficient (ε) of the anthracene derivative that generates the fluorescence is 5000 L · M ⁻¹ · cm ⁻¹ or more as excitation light A fluorescence generation method characterized by providing efficiency. A method of generating fluorescence by irradiating a complex containing at least the pyrene derivative according to claim 2 and a matrix with excitation light including a wavelength band of 300 to 450 nm;
Luminescence with a fluorescence quantum yield (Φ) of 0.8 or more using a wavelength at which the molar extinction coefficient (ε) of the pyrene derivative generating fluorescence is 5000 L · M ⁻¹ · cm ⁻¹ or more as excitation light A fluorescence generation method characterized by providing efficiency. A complex comprising at least the anthracene derivative according to claim 1 and a matrix;
A light irradiation means for irradiating the complex with excitation light;
A laser generator comprising at least amplification means for amplifying light emitted from the complex. In the laser generation, the fluorescence quantum yield (Φ) is 0 using a wavelength at which the molar extinction coefficient (ε) of the anthracene derivative generating the fluorescence is 5000 L · M ⁻¹ · cm ⁻¹ or more as excitation light. 6. The laser generator according to claim 5, wherein the laser generator is 8 or more. A complex comprising at least a pyrene derivative according to claim 2 and a matrix;
A light irradiation means for irradiating the complex with excitation light;
A laser generator comprising at least amplification means for amplifying light emitted from the complex. In the laser generation, the fluorescence quantum yield (Φ) is 0 using a wavelength at which the molar extinction coefficient (ε) of the pyrene derivative generating fluorescence is 10000 L · M ⁻¹ · cm ⁻¹ or more as excitation light. The laser generator according to claim 7, wherein the laser generator is .8 or more.

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