JP4000379B2 - Organic light emitting material - Google Patents

Description

  The present invention relates to a novel organic light emitting material, and more particularly to a stilbene compound that is highly useful as an organic light emitting material for an organic solid-state laser.

  In recent years, organic electroluminescence and organic solid-state lasers have been developed, but there are many problems that require further improvements including light-emitting materials.

  With regard to the problem of light emitting materials, many compounds have been proposed as organic electroluminescent light emitting materials, but the generation of laser light emission at a low threshold and high laser light emission intensity required as light emitting materials for organic solid-state lasers have been proposed. In view of the above, as a light emitting material for an organic solid-state laser (organic solid-state laser light emitting element), a light-emitting material having sufficient characteristics has not yet been found.

  In Patent Document 1, as a compound that can be used as a light emitting material of an organic solid-state laser, a para-polyphenylene compound, a benzothiazole compound, a benzimidazole compound, a benzoxazole compound, a metal chelated oxinoid compound, styrylbenzene Compounds, aromatic dimethylidin compounds, aluminum complexes in which a phenolate ligand and a substituted quinolylate ligand are bonded, styrylamine derivatives, and the like are described.

  Non-Patent Document 1 describes a fluorescent dye having a linear structure as a light emitting material for organic solids (laser dye).

  Non-Patent Document 2 describes a fluorescent dye having a symmetric or asymmetric structure as a light emitting material (laser dye) for organic solids.

Patent Document 2 describes a triarylboron compound as a dye for a scintillation counter.
JP 2000-156536 A US Pat. No. 3,758,412 Chemistry Letters vol.32, No.10 (2003), 968-969 Journal of Photochemistry and Photobiology A: Chemistry 158 (2003), 219-221

  The present invention has been completed in the process of searching for a novel stilbene compound exhibiting excellent characteristics as a light emitting material for an organic solid-state laser.

  The inventors' research has found that a novel boron-containing stilbene compound having a specific chemical structure represented by the following formula (I) exhibits excellent characteristics particularly as a light emitting material for an organic solid-state laser.

［但し、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹、およびＲ¹²は、互いに独立に、水素原子もしくは置換基を表わし、Ｑ¹、Ｑ²、Ｑ³、およびＱ⁴は、互いに独立に、置換基を有していてもよい炭素原子数５以上で、異種原子を含んでいてもよい脂肪族基、脂環族基、もしくは芳香族基を表わし、そしてｎは０〜４の整数である］

[However, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² are each independently a hydrogen atom or a substituent Q ¹ , Q ² , Q ³ , and Q ⁴ are each independently an aliphatic group having 5 or more carbon atoms which may have a substituent and optionally containing a hetero atom, Represents a cyclic group or an aromatic group, and n is an integer of 0 to 4.]

  Since the boron-containing stilbene compound of the present invention exhibits excellent laser emission characteristics (low threshold and / or high emission intensity, and preferable narrow half width of emission spectrum), it is particularly effective as a light-emitting material for organic solid-state lasers. Can be used.

  Preferred compounds as the boron-containing stilbene compound useful as the light emitting material of the present invention are as follows.

(1) R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R ^{12 in} formula (I) are independently from each other; A hydrogen atom, a hydrocarbon group or an alkoxy group;
(2) R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R ^{12 in} formula (I) are independently from each other; A hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms.
(3) R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R ^{12 in} formula (I) are all hydrogen atoms is there.
(4) Q ¹ , Q ² , Q ³ and Q ^{4 in the} formula (I) each independently represent an aromatic hydrocarbon group having 5 or more carbon atoms which may have a substituent.
(5) An aryl group or arylalkyl in which Q ¹ , Q ² , Q ³ , and Q ^{4 in} formula (I) may each independently have an alkyl group having 1 to 6 carbon atoms as a substituent Represents a group.
(6) R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² are each independently a hydrogen atom or carbon atom Represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and Q ¹ , Q ² , Q ³ , and Q ⁴ are each independently an alkyl group having 1 to 6 carbon atoms as a substituent. It represents a phenyl group or a naphthyl group having 1 to 5 (preferably 3) (preferably a methyl group or an ethyl group).

  The boron-containing stilbene compound of the present invention can be obtained, for example, by a method in which trans-dibromostilbene, which is a known compound, is treated with n-butyllithium and then reacted with dimesitylfluoroborane. Note that trans-dibromostilbene can be synthesized from the corresponding phosphonate and aldehyde using the Horner-Wadsworth-Emmons reaction. An example of this reaction scheme is shown below.

  In the formula (I), a compound in which n is 1 is obtained by converting p-bromobenzaldehyde into diethyl acetal, reacting this diethyl acetal with n-butyllithium and dimesitylfluoroborane, and then using an aqueous ammonium chloride solution. The aldehyde compound is obtained by treatment, and can be synthesized in a high yield by reacting the bisphosphonate with the Horner-Wadsworth-Emmons. The reaction scheme is shown below.

In addition, the geometric structure of the double bond site | part of the boron containing stilbene type compound of this invention can be confirmed by the comparison of the value of the chemical shift and the coupling constant in the < ¹ > H-NMR spectrum with the following compound which has a similar structure.

[Example 1] Synthesis of trans-4,4'-bis (dimesitylboryl) stilbene (1) Synthesis of diethyl p-bromobenzylphosphonate p-bromobenzyl bromide (24.99 g, 100 mmol) and triethyl phosphite ( 16.62 g (100 mmol) was stirred at an oil bath temperature of 170 ° C. for 18 hours. Subsequently, the obtained reaction mixture was distilled under reduced pressure to obtain diethyl p-bromobenzylphosphonate (25.13 g, yield: 82%, boiling point: 157 to 160 ° C./4 mmHg) as a colorless liquid.

IR (neat, cm ⁻¹ ): 1492, 1408, 1394, 1250, 1054, 1036, 970, 856, 766
¹ H-NMR (CDCl ₃ , 400 MHz) δ: 7.34 (2H, d, J = 8.5 Hz), 7.09 (2H, dd, J = 8.5, 2.5 Hz), 3.94 ( 4H, m), 3.01 (2H, d, J = 21.5 Hz), 1.17 (6H, t, J = 7.0 Hz)
EI-MS m / z: 308 (M ⁺ ), 306 (M ⁺ )

(2) Synthesis of trans-4,4′-dibromostilbene In a dry ice-acetone bath under an argon atmosphere, a solution of diisopropylamine (3.04 g, 30.0 mmol) in anhydrous tetrahydrofuran (100 mL) was mixed with n-butyllithium. N-hexane solution (1.58M, 16.5 mL, 26.1 mmol) was added dropwise over 3 minutes and stirred in an ice bath for 30 minutes. The obtained reaction mixture was placed in a dry ice-acetone bath with a solution of diethyl p-bromobenzylphosphonate (7.99 g, 26.0 mmol) obtained in (1) above in anhydrous tetrahydrofuran (50 mL) over 15 minutes. Added dropwise and stirred for 30 minutes. A solution of p-bromobenzaldehyde (3.70 g, 20.0 mmol) in anhydrous tetrahydrofuran (50 mL) was added dropwise thereto over 10 minutes, and the mixture was stirred at room temperature for 12 hours. Water (100 mL) was added to the resulting reaction mixture, and the mixture was concentrated under reduced pressure. The precipitated solid was collected by suction filtration, then washed successively with water and methanol, and trans-4,4′-dibromostilbene (5 .28 g, yield: 78%, melting point: 214-215 ° C.) as a white solid.

IR (KBr, cm ⁻¹ ): 1584, 1490, 1402, 1074, 1006, 970, 820
¹ H-NMR (CDCl ₃ , 400 MHz) δ: 7.48 (4H, d, J = 8.5 Hz), 7.36 (2H, d, J = 8.5 Hz), 7.02 (2H, s)
EI-MS m / z: 340 (M ⁺ ), 338 (M ⁺ ), 336 (M ⁺ )

(3) Synthesis of (E, E) -1,4-bis [2- (p-bromophenyl) ethenyl] benzene Diisopropylamine (3.04 g, 30.0 mmol) in a dry ice-acetone bath under argon atmosphere ) Was added dropwise over a period of 3 minutes to a solution of n-butyllithium in n-hexane (1.58M, 15.8 mL, 25.0 mmol) in an anhydrous tetrahydrofuran (100 mL) solution and stirred in an ice bath for 30 minutes. To the resulting reaction mixture, a solution of diethyl p-bromobenzylphosphonate (7.68 g, 25.0 mmol) obtained in (1) above in anhydrous tetrahydrofuran (50 mL) was added dropwise over 15 minutes in a dry ice-acetone bath. And stirred for 30 minutes. To this, a solution of terephthalaldehyde (0.81 g, 6.0 mmol) in anhydrous tetrahydrofuran (50 mL) was added dropwise over 10 minutes, and the mixture was stirred at room temperature for 12 hours. Water (20 mL) was added to the resulting reaction mixture, and the precipitated solid was collected by suction filtration, washed in turn with water and methanol, and (E, E) -1,4-bis [2- (p-bromophenyl). ) Ethenyl] benzene (2.41 g, yield: 91%, melting point:> 300 ° C.) was obtained as a yellow solid.

IR (KBr, cm ⁻¹ ): 1580, 1510, 1484, 1418, 1398, 1076, 1008, 970, 828
¹ H-NMR (DMSO-d ₆ , 400 MHz) δ: 7.62 (4H, s), 7.56 (8H, s), 7.30 (2H, d, J = 16.5 Hz), 7.27 (2H, d, J = 16.5Hz)

(4) Synthesis of trans-4,4′-bis (dimesitylboryl) stilbene Trans-4,4′-dibromostilbene (1.86 g, obtained in (2) above in a dry ice-acetone bath under an argon atmosphere. To a solution of 5.5 mmol) in anhydrous tetrahydrofuran (100 mL), n-butyllithium in n-hexane (1.58 M, 9.1 mL, 14.4 mmol) was added dropwise over 5 minutes, and the mixture was stirred for 1 hour. A solution of dimesitylfluoroborane (90%, 4.95 g, 16.6 mmol) in anhydrous tetrahydrofuran (30 mL) was added dropwise to the obtained reaction mixture over 10 minutes, stirred for 30 minutes, and then stirred at room temperature for 12 hours. did. Water (100 mL) was added to the resulting reaction mixture, and the mixture was concentrated under reduced pressure. Chloroform (200 mL) was added to the residue, and the organic layer was separated. The aqueous layer was extracted with chloroform (3 × 50 mL), the organic layer and the extract were combined, then washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. Magnesium sulfate was filtered off, the filtrate was concentrated under reduced pressure, the residue was separated by column chromatography (silica gel, toluene / hexane = 1/3), recrystallized from chloroform-ethanol, and trans-4,4'- Bis (dimesitylboryl) stilbene (1.97 g, yield: 53%, melting point: 262-264 ° C.) was obtained as colorless needle crystals.

IR (KBr, cm ⁻¹ ): 1598, 1420, 1240, 1218, 1176, 844
¹ H-NMR (CDCl ₃ , 400 MHz) δ: 7.51 (4H, d, J = 8.0 Hz), 7.48 (4H, d, J = 8.0 Hz), 7.22 (2H, s) 6.82 (8H, s), 2.31 (12H, s), 2.02 (24H, s)
¹³ C-NMR (CDCl ₃ , 100 MHz) δ: 145.6, 141.7, 140.8, 140.5, 138.6, 137.0, 130.2, 128.2, 126.2, 23. 4, 21.2
HR-MS: 676.4443 (measured value) [Calculated _{(C 50 H 54 B 2)} : 676.4412

Example 2 Synthesis of (E, E) -1,4-bis [2- (p-dimesitylborylphenyl) ethenyl] benzene In a dry ice-acetone bath under an argon atmosphere, To the mixture of (E, E) -1,4-bis [2- (p-bromophenyl) ethenyl] benzene (2.38 g, 5.4 mmol) obtained in 3) and anhydrous tetrahydrofuran (100 mL) was added n-butyl. Lithium n-hexane solution (1.58 M, 8.9 mL, 14.1 mmol) was added dropwise over 5 minutes, and the mixture was stirred for 1 hour. To the resulting reaction mixture, a solution of dimesitylfluoroborane (90%, 4.81 g, 16.1 mmol) in anhydrous tetrahydrofuran (30 mL) was added dropwise over 10 minutes, stirred for 30 minutes, and then stirred at room temperature for 12 hours. did. Water (100 mL) was added to the obtained reaction mixture, and the mixture was concentrated under reduced pressure. Chloroform (200 mL) was added to the residue, and the insoluble material was filtered off. After separating the organic layer, the aqueous layer was extracted with chloroform (3 × 50 mL), the organic layer and the extract were combined, washed with water and saturated brine in that order, and dried over anhydrous magnesium sulfate. Next, magnesium sulfate was filtered off, and the filtrate was concentrated under reduced pressure. The residue was separated by column chromatography (silica gel, toluene / hexane = 1/3) and recrystallized from chloroform-ethanol to give (E, E) -1,4-bis [2- (p-di Mesitylborylphenyl) ethenyl] benzene (0.05 g, yield: 1%, melting point: 299-301 ° C.) was obtained as yellow needle crystals.

IR (KBr, cm ⁻¹ ): 1590, 1418, 1240, 1220, 1170, 842
¹ H-NMR (CDCl ₃ , 400 MHz) δ: 7.53 (4H, s), 7.51 (4H, d, J = 8.0 Hz), 7.48 (4H, d, J = 8.0 Hz) 7.20 (2H, d, J = 16.5 Hz), 7.15 (2H, d, J = 16.5 Hz), 6.83 (8 H, s), 2.31 (12 H, s), 2 .02 (24H, s)
¹³ C-NMR (CDCl ₃ , 100 MHz) δ: 145.4, 141.8, 140.8, 140.7, 138.6, 137.0, 136.8, 129.8, 128.7, 128. 2, 127.1, 126.1, 23.4, 21.2
HR-MS: 778.4857 (measured value), the calculated value _{(C 58 H 60 B 2)} : 778.4881

Example 3 Synthesis of (E, E) -1,4-bis [2- (p-dimesitylborylphenyl) ethenyl] benzene (1) Synthesis of 1-bromo-4- (diethoxymethyl) benzene A mixture of p-bromobenzaldehyde (33.61 g, 182 mmol), ethyl orthoformate (29.61 g, 200 mmol), Amberlyst-15 (10 g), and absolute ethanol (200 mL) was stirred at room temperature for 24 hours. did. The resulting reaction mixture was filtered, the filtrate was concentrated under reduced pressure, and the residue was then distilled under reduced pressure to give 1-bromo-4- (diethoxymethyl) benzene (45.28 g, yield: 96%, boiling point: 90-91 ° C./0.6 mmHg) was obtained as a colorless liquid.

IR (KBr, cm ⁻¹ ): 1714, 1592, 1488, 1396, 1336, 1272, 1204, 1112, 1052, 1014, 798
¹ H-NMR (CDCl ₃ , 400 MHz) δ: 7.48 (2H, d, J = 8.5 Hz), 7.35 (2H, d, J = 8.5 Hz), 5.46 (1H, s) 3.56 (4H, m), 1.23 (6H, t, J = 7.0 Hz)
EI-MS m / z: 260 (M ⁺ ), 258 (M ⁺ )

(2) Synthesis of p- (dimesitylboryl) benzaldehyde 1-Bromo-4- (diethoxymethyl) benzene (31.10 g, 120 mmol) obtained in (1) above in a dry ice-acetone bath under an argon atmosphere N-Butyllithium solution in n-butyllithium (1.59 M, 83 mL, 132 mmol) was added dropwise over 20 minutes to an anhydrous tetrahydrofuran (150 mL) solution and stirred for 1 hour. To the obtained reaction mixture, a solution of dimesitylfluoroborane (90%, 29.80 g, 100 mmol) in anhydrous tetrahydrofuran (100 mL) was added dropwise over 20 minutes, stirred for 30 minutes, and then stirred at room temperature for 16 hours. did. A saturated aqueous ammonium chloride solution (100 mL) was added to the obtained reaction mixture, and the mixture was concentrated under reduced pressure. The residue was extracted with chloroform (3 × 100 mL). The extract was washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate. Magnesium sulfate was filtered off, and the filtrate was concentrated under reduced pressure. The residue was recrystallized from 2-propanol to obtain p- (dimesitylboryl) benzaldehyde (31.18 g, yield: 88%, melting point: 175 to 176 ° C.) as colorless plate crystals.

IR (KBr, cm ⁻¹ ): 1708, 1604, 1550, 1420, 1240, 1210, 850, 814, 720
¹ H-NMR (CDCl ₃ , 400 MHz) δ: 10.07 (1H, s), 7.83 (2H, d, J = 8.0 Hz), 7.65 (2H, d, J = 8.0 Hz) 6.83 (8H, s), 2.32 (6H, s), 1.97 (12H, s)
¹³ C-NMR (CDCl ₃ , 100 MHz) δ: 192.6, 152.8, 141.4, 140.8, 139.4, 138.0, 135.9, 129.0, 128.4, 23. 4, 21.2
EI-MS m / z: 354 (M ⁺ )

(3) Synthesis of (E, E) -1,4-bis [2- (p-dimesitylborylphenyl) ethenyl] benzene p- (Dimesitylboryl) benzaldehyde (7.79 g, 22.0 mmol) under argon atmosphere ), Tetraethyl p-xylylene phosphonate (3.78 g, 10.0 mmol), and anhydrous dimethylformamide (80 mL) in a mixed solution of potassium tert-butoxide (4.49 g, 40.0 mmol) in anhydrous dimethylformamide. The (30 mL) solution was added dropwise over 20 minutes and stirred at room temperature for 24 hours. Methanol (2000 mL) was added to the obtained reaction mixture, and the mixture was stirred at room temperature for 1 hour, and the precipitated solid was subjected to suction filtration. The obtained solid was separated by column chromatography (silica gel, toluene / hexane = 1/3) and then recrystallized from chloroform-ethanol to give (E, E) -1,4-bis [2- (p- Dimesitylborylphenyl) ethenyl] benzene (7.16 g, yield: 92%, melting point: 301.0-302.5 ° C.) was obtained as yellow needle crystals.

[Example 4] Confirmation of laser emission (1) Trans-4,4'-bis (dimesitylboryl) stilbene (hereinafter referred to as Compound 1 of the present invention) synthesized in Example 1 and Example 3 (E, E) 1,4-bis [2- (p-dimesitylborylphenyl) ethenyl] benzene (hereinafter referred to as the present compound 2) is 4.8% by mass with respect to polycarbonate (PC-BisZ). Doping was performed at a ratio, and spin coating was performed on a quartz glass substrate so that the film thickness was about 200 mm. Next, N ₂ gas laser light was irradiated from a direction perpendicular to the quartz glass with a film, and emission of light from the end face of the quartz glass was detected.

  Table 1 shows the results of the absorption spectrum, fluorescence spectrum, and ASE (amplified spontaneous emission light) spectrum of the light emitted from the end face of the quartz glass. In addition, the compounds 1 and 2 of the present invention have the same basic skeleton, and a comparative compound 1 and a comparative compound 2 in which a nitrogen atom is inserted instead of a boron atom (the chemical structural formula is described below in Table 1). The results of the absorption spectrum, fluorescence spectrum, and ASE spectrum of the laser light are also shown in Table 1.

Table 1 ────────────────────────────────────
Compound Absorption / fluorescence spectrum ASE spectrum
Abs PL threshold λ _max FWHM Luminescence intensity
(λ _max nm) (λ _max nm) (μJ / cm ² ) (nm) (nm) (x10 ⁴ cnt.)
────────────────────────────────────
Invention 1 374 412 8 433 2.0 27
Comparison 1 392 442 11 463 5.4 35
────────────────────────────────────
Invention 2 400 449 18 472 2.0 116
Comparison 2 418 484 16 507 6.0 60
────────────────────────────────────

  From the results in Table 1, it can be seen that the boron-containing stilbene compound of the present invention exhibits high laser emission intensity at a low threshold. It was also confirmed that the boron-containing stilbene compound of the present invention exhibits a very small half width (FWHM). That is, the boron-containing stilbene compound of the present invention exhibits laser emission exhibiting high laser emission intensity at a low threshold comparable to that of a known nitrogen-containing stilbene compound, and its emission spectrum is compared with that of a known nitrogen-containing stilbene compound. Clearly showing a small value.

Claims (13)

Formula (I) below:

[However, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² are each independently a hydrogen atom or a substituent Q ¹ , Q ² , Q ³ , and Q ⁴ are each independently an aliphatic group having 5 or more carbon atoms which may have a substituent and optionally containing a hetero atom, Represents a cyclic group or an aromatic group, and n is an integer of 0 to 4.]
A luminescent material comprising a boron-containing stilbene compound represented by: R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R ^{12 in} formula (I) are each independently a hydrogen atom, The luminescent material according to claim 1, which is a hydrocarbon group or an alkoxy group. R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R ^{12 in} formula (I) are each independently a hydrogen atom, The luminescent material according to claim 2, which is an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms. R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R ^{12 in} formula (I) are all hydrogen atoms. 4. The luminescent material according to 3. The Q ¹ , Q ² , Q ³ , and Q ^{4 in the} formula (I) each independently represent an optionally substituted aromatic hydrocarbon group having 5 or more carbon atoms. Luminescent material. Q ¹ , Q ² , Q ³ , and Q ^{4 in} formula (I) each independently represent an aryl group or arylalkyl group optionally having an alkyl group having 1 to 6 carbon atoms as a substituent. The luminescent material according to claim 1. A boron-containing stilbene compound represented by the following formula (I):

[However, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² are
Each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Q ¹ , Q ² , Q ³ , and Q ⁴ are each independently an alkyl group having 1 to 6 carbon atoms as a substituent. 1 to five with a phenyl group or a naphthyl group and Table Wa, and n is an integer of 0 to 4]. An organic solid-state laser comprising a boron-containing stilbene compound represented by the following formula (I) as a light emitting material:

[However, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² are each independently a hydrogen atom or a substituent Q ¹ , Q ² , Q ³ , and Q ⁴ are each independently an aliphatic group having 5 or more carbon atoms which may have a substituent and optionally containing a hetero atom, Represents a cyclic group or an aromatic group, and n is an integer of 0 to 4]. R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R ^{12 in} formula (I) are each independently a hydrogen atom, The organic solid-state laser according to claim 8, which is a hydrocarbon group or an alkoxy group. R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R ^{12 in} formula (I) are each independently a hydrogen atom, The organic solid-state laser according to claim 9, which is an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms. R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R ^{12 in} formula (I) are all hydrogen atoms. 10. An organic solid-state laser as described in 10. The Q ¹ , Q ² , Q ³ , and Q ^{4 in the} formula (I) each independently represent an aromatic hydrocarbon group having 5 or more carbon atoms that may have a substituent. Organic solid-state laser. Q ¹ , Q ² , Q ³ , and Q ^{4 in} formula (I) each independently represent an aryl group or arylalkyl group optionally having an alkyl group having 1 to 6 carbon atoms as a substituent. The organic solid-state laser according to claim 8.