KR100821889B1 - Novel fluorophores and a preparing method thereof - Google Patents

Abstract

The present invention relates to a novel fluorescent substance and a method for producing the same, specifically 1,4-bis (dibromovinyl) benzene (1,4-bis [dibromovinyl] benzene) and 2,5-bis (dibromo vinyl) The present invention relates to a novel fluorescent substance represented by the following Chemical Formula 1 synthesized by Sonogashira reaction of thiophene (2,5-bis [bromovinyl] thiophene), and a method for preparing the same. The fluorescent material of the present invention exhibits a maximum emission range from indigo blue to reddish orange depending on the aromatic nuclei and peripheral moieties, and thus is a tunable fluorescent material in the field of electrons and photons. It can be usefully used.

Description

New fluorescent substance and its manufacturing method {NOVEL FLUOROPHORES AND A PREPARING METHOD THEREOF}             

1 is a result of analyzing the fluorescence emission spectrum of the novel fluorescent materials synthesized according to the present invention.

A; Emission Spectrum of Phosphors 12a , 12d , 12c and 12d

B; Emission Spectrum of Phosphors 13a , 13d , 13c and 13d

C; Visualized emission of phosphors 12a , 12d , 13a and 13d

The present invention relates to a novel fluorescent substance and a method for producing the same, specifically 1,4-bis (dibromovinyl) benzene (1,4-bis [dibromovinyl] benzene) and 2,5-bis (dibromo vinyl) The present invention relates to a novel fluorescent substance represented by the following Chemical Formula 1 synthesized by Sonogashira reaction of thiophene (2,5-bis [bromovinyl] thiophene), and a method for preparing the same.

<Formula 1>

Recently, organic compounds having high photoluminescence properties have been of interest in various research fields as advanced materials for the application of electronic and optical engineering. Therefore, it is very important to efficiently synthesize novel chemically functionalized and modified new phosphors, which is essential for obtaining materials with modifiable optoelectronic properties.

It is known to prepare various fluorescent materials using 1,1-dibromo-1-alkenes. For example, to from 1,1-dibromo-1-alkene 1, as shown in Scheme 1 (Z) -1-bromo-1-alkane ([Z] -bromo-1- alkanes) 2 (Uenishi, J., Kawahawa, R., Yonemitsu, O., J. Org.Chem. 63: 8965, 1998), (Z) -1-aryl (alkenyl) -1-bromo-1-alkene ([Z] -1-aryl [alkenyl] -1-bromo-1-alkenes) 3 (Roush, WR, Moriarty, KJ, Brown, BB, Tetrahedron lett . 45: 6509, 1998), 1,1- diar (alkenyl) 1,1-diar [alkenyl] -1-alkenes) 4 (Shen, W., and Wang, L J. Org. Chem . 64: 8873, 1999) and 1,3-diyne (1, 3-diynes) 6 (Shen, W., Thomas, SA, Org. Lett . 2: 2857, 2000).

However, there are no examples of research for the development of fluorescent materials through the synthesis route to compound 7 .

Accordingly, the present inventors have studied to change the conjugated bond length and substituents of 1,1-dibromo-1-alkene to prepare a new modifiable fluorescent substance. As a result, 1,4-bis (dibromovinyl) benzene ( Sonogashira reaction of 1,4-bis [dibromovinyl] benzene) and 2,5-bis (dibromovinyl) thiopene (2,5-bis [dibromovinyl] thiopene) provides excellent fluorescence over a wide wavelength range Knowing that it can provide a fluorescent material has been completed the present invention.

SUMMARY OF THE INVENTION An object of the present invention is to provide a fluorescent material having excellent photoluminescence properties that can be applied to various electronic and optical fields.

In order to achieve the above object, the present invention is a fluorescent material through the reaction of other aromatic bromide with 1,4-bis (dibromovinyl) benzene and 2,5-bis (dibromovinyl) thiophene It provides a method for efficiently preparing and a novel fluorescent material synthesized therefrom.

Hereinafter, the present invention will be described in detail.

According to the present invention, the compound of Formula 1 can be obtained through the Sonogashira reaction as in Scheme 2 below.

Wherein A and B are as defined in formula (1) .

Compound 8 of Scheme 2 used as a starting material in the present invention may be obtained by a known method (Corey, EJ and Fuchs, PL, Tetrahedron lett . 4831, 1972), for example, as in Scheme 3 below.

That is, the dialdehyde compound is reacted with CBr ₄ and PPh _{3 in a} solvent such as CH ₂ Cl ₂ at room temperature to give 1,4-bis (dibromovinyl] benzene) or 2, Dibromoalkenes of 5-bis (dibromovinyl) thiophene (2,5-bis [dibromovinyl] thiopene) can be obtained.

Specifically, as shown in step a), (PPh ₃ ) ₂ PdCl ₂ , the catalyst CuI and Et ₃ N, by the Sonogashira reaction of dibromoalkenes with phenylacetylene in a solvent, represented by the formula (2 ) Phenylacetylene is added to dibromoalkene of 8 , and the mixture is stirred at 45 to 50 ° C., the resulting mixture is evaporated, and then the residue is subjected to column chromatography to obtain a compound of formula 1 . The process according to step a) is used when B in the compound of Formula 1 is a phenyl group.

Wherein A is as defined in formula (1) .

인 경우는 상기 화합물 9를 (PPh₃)₂PdCl₂, 촉매 CuX 및 Et₂NH/MeOH 용매 존재하에서 KF 및 브로모티오펜과 45 내지 50℃에서 교반하면서 반응시킴으로써 화학식 1의 화합물을 수득할 수 있다. When B is the remaining functional group other than phenyl in the compound of Formula 1 , it is prepared by a modified Sonogashira reaction between TMS-protected tetraalkyne and aromatic bromide, as in steps b and c. Trimethylsilylacetylene, (PPh ₃ ) ₂ PdCl ₂ , catalyst CuX (where X = Cl or I) and Et ₃ N / MeOH were mixed with dibromoalkene of 8 and stirred at 45 to 50 ° C., and the resulting mixture was stirred. After evaporation, the residue was subjected to column chromatography to obtain Intermediate Compound 9 represented by the following Chemical Formula 3 (Step b).

The case may give a compound of formula (I) by reacting with under the above compound 9 a (PPh _{3) 2} PdCl _2, catalyst CuX and Et ₂ NH / MeOH solvent present stirred at KF and-bromothiophene and 45 to 50 ℃ .

Wherein A is as defined in formula (1) .

인 경우는 상기 화합물 9를 (PPh₃)₂PdCl₂, 촉매 CuX 및 Et₃N/MeOH 용매 존재하에서 KF 및 아릴브로마이드와 45 내지 50℃에서 교반하여 반응시킴으로써 화학식 1의 화합물을 수득할 수 있다. In addition, B is another functional group

The case may give a compound of formula (I) by reaction by stirring the compound 9 (PPh _{3) 2} PdCl _2, catalyst CuX and KF and an aryl bromide and from 45 to 50 ℃ under Et ₃ N / MeOH solvent present.

The method consists of the in situ liberation of alkyne from the corresponding TMS-protecting compound in the presence of KF and the coupling of the aromatic bromide compound, eliminating the TMS-deprotection and purification steps. It is very suitable for the connection of unstable or volatile alkynes.

The structures of the fluorescent materials 10 to 13e synthesized by the preparation method were determined by ¹ H NMR, ¹³ C NMR spectroscopy, mass spectrometry, and elemental analysis. As a result, the fluorescent materials 12a to 13e of the present invention are represented by the following formulas, respectively. It has a structure.

Fluorescent substance 12a

Fluorescent substance 12b

Fluorescent substance 12c

Fluorescent material 12d

Fluorescent substance 12e

Fluorescent substance 13a

Fluorescent substance 13b

Fluorescent material 13c

Fluorescent material 13d

Fluorescent substance 13e

The compound of formula 1 and intermediate compound 9 of formula 3 according to the invention are fairly stable with respect to air and commonly used organic solvents. In order to investigate the photophysical properties of the fluorescent materials 12a to 13e on the CHCl ₃ solution, the fluorescence quantum yields (Φ _F ) of the fluorescent materials were determined (Parker, CA, In Photoluminescence of Solutions, Elsevier , Amsterdam, 1968), phosphors 12a and 12b had a medium quantum yield and the longest fluorescence life time (τ _S ) of all phosphors (see Table 1 ).

In addition, by analyzing their normalized emission spectra, the absorption maximum represented by the π-π * transition of the phosphor in the UV-visible absorption spectra is found in the central unit of the molecules. 1A and 1B , and emission maximums were also different depending on the aromatic nucleus of the phosphor, ranging from indigo to reddish orange regions (see FIG. 1C ).

As demonstrated above, the novel compounds synthesized by the preparation method of the present invention exhibit dramatic absorption and emission spectra changes and high quantum yields, and thus can be usefully used as modulators in the electronic and photon fields.

Hereinafter, the present invention will be described in detail by way of examples.

However, the following examples are merely to illustrate the invention, but the content of the present invention is not limited to the following examples.

Example 1 Synthesis of Novel Fluorescent Materials by Sonogashira Reaction

(1-1) Intermediate Compound 10

675.3 mg (1.51 mmol) of Compound 8 dissolved in Et ₃ N (30 mL) 8 , 1.3 mL (9.20 mmol) of (trimethylsilyl) acetylene, 213 mg (0.303 mmol) of (PPh ₃ ) ₂ PdCl ₂ , 39.8 mg (0.152 mmol) of CuI mixture was stirred at 45-50 ° C. After stirring for 2 hours, the mixture was evaporated. Column chromatography (Column chromatography [SiO ₂ , hexane]) was carried out to give 714 mg (91%) of compound 10 in a solid form.

m.p. 118 to 120 ° C;

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.86 (s, 4H; ArH), 7.04 (s, 2H; CCH), 0.27 and 0.24 (2s, 36H; SiCH ₃ );

¹³ C NMR (75 MHz, CDCl ₃ ) δ 144.1, 136.2, 128.9, 104.2, 103.8, 102.2, 101.7, 94.2, -0.2, -0.3;

MS (FAB, m / z) 514.3 (M &lt; + &gt;);

UV (CHCl ₃ ): λ max (ε × 10 ⁻⁵ ) = 412 (4.7);

Elemental anal. Calcd. for C ₃₀ H ₄₂ Si ₄ H _{2 O} : C, 67.60;

H, 8.32. Found: C, 67.30;

H, 8.19.

(1-2) Intermediate Compound 11

198 mg (0.442 mmol) of Compound 9 , 749 μl (5.30 mmol) of (trimethylsilyl) acetylene, 62.0 mg (0.088 mmol) of (PPh ₃ ) ₂ PdCl ₂ , 17.0 mg dissolved in Et ₃ N (8.8 mL) (0.088 mmol) of CuI mixture was stirred at 45-50 ° C. After stirring for 3 hours, the mixture was evaporated. Column chromatography (SiO ₂ , hexane) was performed to obtain 210 mg (91%) of compound 11 .

m.p. 146 to 148 ° C;                     

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.62 (s, 4H; ArH), 7.07 (s, 2H; CCH), 0.26 and 0.19 (2s, 36H; SiCH ₃ );

¹³ C NMR (75 MHz, CDCl ₃ ) δ 141.4, 136.8, 130.0, 104.9, 103.7, 102.0, 101.9, 95.4, -0.2, -0.4;

MS (FAB, m / z) 520.2 (M &lt; + &gt;);

UV (CHCl ₃ ): λ max (ε 10 ⁻⁵ ) = 458 (4.8);

Elemental anal. Calcd. for C ₂₈ H ₄₀ S ₁ Si ₄ : C, 64.55;

H, 7.74. Found: C, 64.20;

H, 7.99.

(1-3) Fluorescent substance 12a

To a solution of Compound 8 (322 mg, 0.722 mmol) and phenyl acetylene (1.2 mL, 11.6 mmol) dissolved in Et ₃ N / MeOH (2 mL / 8 mL) (PPh ₃ ) ₂ PdCl ₂ (76 mg, 0.108 mmol) and CuI (21 mg, 0.108 mmol) were added. The mixture was stirred at 45-50 ° C. for 3 hours. After evaporation of the mixture in vacuo ( in Vacuo ), the residue was chromatographed on a silica gel column using hexane as an eluent to obtain compound 12a (299 mg, 60%).

m.p. 182 to 185 ° C;

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.98 (s, 4H; ArH), 7.55-7.52 (m, 8H; ArH), 7.38 (m, 12H; ArH), 7.15 (s, 2H; CCH);

¹³ C NMR (75 MHz, CDCl ₃ ) δ 142.2, 131.7, 131.6, 129.0, 128.8, 128.5, 128.3, 125.9;

MS (FAB, m / z) 530.2 (M &lt; + &gt;);

UV (CHCl ₃ ): λ max (ε 10 ⁻⁵ ) = 416 (5.5);

Elemental anal. Calcd. _{for C 42 H 26 0. 5 H} 2 O: C, 93.48;

H, 5.04. Found: C, 93.44;

H, 4.87.

(1-4) fluorescent substance 12b

111 mg (0.216 mmol) of compound 10 , 0.3 mL (3.10 mmol) of 2-bromothiophene, 141 mg (2.51 mmol) dissolved in Et ₂ NH / MeOH (25 mL / 6.3 mL) KF, 44 mg (0.0627 mmol) of (PPh ₃ ) ₂ PdCl ₂ and 12 mg (0.063 mmol) of CuI mixture was stirred at 45-50 ° C. After stirring for 4 hours, the mixture was evaporated. Column chromatography (SiO ₂ , hexane: ethyl acetate, 20: 1) was performed to obtain 54.5 mg (45%) of compound 12b in solid form.

m.p. 190 to 191 ° C;

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.92 (s, 4H; ArH), 7.33 (m, 8H; ThH), 7.11 (s, 2H; C = CH), 7.03-6.99 (m, 4H; ThH) ;

¹³ C NMR (75 MHz, CDCl ₃ ) δ 142.1, 136.4, 132.7, 132.5, 129.1, 128.4, 127.8, 127.3, 127.2, 122.7, 103.4, 92.5, 90.7, 89.2, 82.7;

MS (FAB, m / z) 553.9 (M &lt; + &gt;);

UV (CHCl ₃ ): λ max (ε 10-5) = 438 (6.0);

Elemental anal. Calcd. for C ₃₄ H ₁₈ S ₄ : C, 73.61;

H, 3.27. Found: C, 73.95;

H, 3.13.

(1-5) Fluorescent substance 12c

98.1 mg (0.191 mmol) of compound 10 dissolved in Et ₃ N / MeOH (14.3 mL / 4.8 mL) 10 , 88 mg (1.52 mmol) of 5-bromo-2-furaldehyde , 267 mg (1.53 mmol) of KF, 27 mg (0.0385 mmol) of (PPh ₃ ) ₂ PdCl ₂ and 2 mg (0.020 mmol) of CuCl mixture were stirred at 45-50 ° C. After stirring for 5 hours, the mixture was evaporated. Column chromatography (SiO ₂ , hexane: ethyl acetate, 1: 1) was performed to obtain 43 mg (38%) of compound 12c in solid form.

m.p. > 131 ° C;

¹ H NMR (300 MHz, CDCl ₃ ) δ 9.66 (s, 4H; CHO), 7.96 (s, 4H; ArH), 7.31-7.25 (m, 10H; FuH and C = CH);

¹³ C NMR (75 MHz, CDCl ₃ ) δ 177.2, 153.0, 152.8, 145.6, 141.1, 136.4, 129.7, 125.9, 121.3, 118.7, 118.0, 101.4, 94.6, 92.2, 87.2, 85.3;

UV (CHCl ₃ ): λ max (ε 10 ⁻⁵ ) = 450 (4.5);

Elemental anal. Calcd. for C ₃₈ H ₁₈ O ₈ : C, 75.75;

H, 3.01. Found: C, 75.52;

H, 3.00.

(1-6) fluorescent substance 12d

Compound 10 (144 mg, 0.28 mmol) and 5-bromo-2-thiophenecarboxaldehyde (5-bromo-2-thiophenecarboxaldehyde) dissolved in Et ₃ N / MeOH (21 mL / 7 mL) (0.33 mL, 2.78 mmol) was added (PPh ₃ ) ₂ PdCl ₂ (39 mg, 0.0556 mmol) and CuI (5 mg, 0.0263 mmol). The mixture was stirred at 45-50 ° C. for 5 hours. After evaporation of the solution in vacuo, the residue was subjected to silica gel column chromatography using hexane: ethyl acetate (1: 1) as an eluting solvent to give compound 12d (98.2 mg, 53%). Got it.

m.p. > 146 ° C;

¹ H NMR (300 MHz, CDCl ₃ ) δ 9.88 (s, 4H; CHO), 7.93 (s, 4H; ArH), 7.70 (br d, 4H; ThH), 7.38 (br d, 4H; ThH), 7.24 (s, 2H; C = CH);

¹³ C NMR (75 MHz, CDCl ₃ ) δ 182.4, 182.3, 145.1, 144.7, 144.5, 136.5, 136.2, 135.9, 133.5, 133.2, 131.1, 129.5, 128.2, 102.6, 96.2, 94.0, 88.7, 82.7;

MS (FAB, m / z) 669.9 (M ++ H);

UV (CHCl ₃ ): λ max (ε 10 ⁻⁵ ) = 456 (2.8);

Elemental anal. Calcd. for C ₃₈ H ₁₈ O ₄ S ₄ H ₂ O: C, 66.45;

H, 2.93. Found: C, 66.10;

H, 2.64.

(1-7) Fluorescent substance 12e

To a solution of compound 10 (102 mg, 0.195 mmol) and 4-bromopyridine hydrochloride (384 mg, 1.97 mmol) dissolved in Et ₃ N / MeOH (14.6 mL / 4.9 mL) (PPh ₃ ) ₂ PdCl ₂ (27 mg, 0.0385 mmol) and CuI (4 mg, 0.021 mmol) were added. The mixture was stirred at 45-50 ° C. for 8 hours. After evaporation of the solution in vacuo, the residue was subjected to silica gel column chromatography using ethyl acetate: methyl alcohol (10: 1) as the eluent, to obtain compound 12e (58.1 mg, 56%).

m.p. > 380 ° C .;

¹ H NMR (300 MHz, CDCl ₃ ) δ 8.60 (br d, 8H; J = 4.7 Hz; PyH), 7.94 (s, 4H; ArH), 7.39-7.30 (m, 8H; PyH), 7.27 (s, 2H; C = CH);

¹³ C NMR (75 MHz, CDCl ₃ ) δ 149.9, 149.8, 145.1, 136.4, 130.6, 130.4, 129.4, 125.5, 125.3, 120.9, 95.3, 92.6, 92.3, 90.3;

MS (FAB, m / z) 535.0 (M ++ H);

UV (CHCl ₃ ): λ max (ε 10 ⁻⁵ ) = 420 (0.94);

Elemental anal. Calcd. for C ₃₈ H ₂₂ N ₄ .0.5H ₂ O: C, 83.96;

H, 4. 26; N, 10.30. Found: C, 84.08;

H, 4.09; N, 10.23.

(1-8) fluorescent material 13a

To a solution of compound 9 (232 mg, 0.518 mmol) and phenylacetylene (0.85 mL, 7.77 mmol) dissolved in Et ₃ N / MeOH (2 mL / 8 mL) (PPh ₃ ) ₂ PdCl ₂ (55 mg, 0.0784 mmol) And CuI (15 mg, 0.0788 mmol). The mixture was stirred at 45-50 ° C. for 3 hours. The solution was evaporated in vacuo, and the residue was subjected to silica gel column chromatography using hexane as an eluent to obtain compound 13a (228 mg, 78%).

m.p. 134 to 136 ° C;

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.62-7.56 (m, 8H; ArH), 7.48 (s, 2H; ArH), 7.43-7.39 (m, 6H; ArH), 7.37 (s, 2H; C = CH), 7.28-7. 26 (m, 6H; ArH);

¹³ C NMR (75 MHz, CDCl 3) δ 142.0, 135.6, 131.6, 131.5, 130.6, 128.6, 128.4, 128.3, 128.2, 122.8, 122.4, 101.7, 98.1, 90.0, 89.2, 87.5;

MS (FAB, m / z) 536.1 (M &lt; + &gt;);

UV (CHCl ₃ ): λ max (ε X 10 ^-5 ) = 468 (3.9);

Elemental anal. Calcd. for C ₄₀ H ₂₄ S ₁ : C, 89.52;

H, 4.51. Found: C, 89.23;

H, 4.64.

(1-9) fluorescent substance 13b

107 mg (0.201 mmol) of compound 11 , 0.19 mL (1.96 mmol) of 2-bromothiophene, 90 mg (1.6 mmol) dissolved in Et ₂ NH / MeOH (16 mL / 4 mL) KF, 28 mg (0.0399 mmol) of (PPh ₃ ) ₂ PdCl ₂ and 7.6 mg (0.0399 mmol) of CuI mixture were stirred at 45-50 ° C. The mixture was stirred for 5 hours and then evaporated. Column chromatography (SiO ₂ , hexane: ethyl acetate, 10: 1) was carried out to give 55.2 mg (49%) of solid compound 13b .

m.p. > 126 ° C;

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.35 (s, 2H; ArH), 7.25-7.20 (m, 10H; ArH and C = CH), 6.96 (t, 2H, J = 4.3 Hz; ArH), 6.84 (t, 2H, J = 4.3 Hz; ArH);

¹³ C NMR (75 MHz, CDCl ₃ ) δ 142.1, 135.3, 132.6, 132.4, 130.7, 128.5, 127.8, 127.2, 122.8, 122.3, 101.2, 92.3, 92.0, 91.0, 83.7;

MS (FAB, m / z) 559.8 (M &lt; + &gt;);

UV (CHCl ₃ ): λ max (ε × 10 ⁻⁵ ) = 486 (5.1);

Elemental anal. Calcd. for C ₃₂ H ₁₆ S ₅ : C, 68.54;

H, 2.88. Found: C, 68.54;

H, 3.03.                     

(1-10) fluorescent substance 13c

69.2 mg (0.13 mmol) of compound 11 , 182 mg (1.04 mmol) 5-bromo-2-furaldehyde, 75 mg (1.29 mmol) KF dissolved in Et ₃ N / MeOH (9.7 mL / 3.2 mL) , 18 mg (0.0256 mmol) of (PPh ₃ ) ₂ PdCl ₂ and 2.6 mg (0.0263 mmol) of CuCl mixture were stirred at 45-50 ° C. After stirring for 5 hours the mixture was evaporated. Column chromatography (SiO ₂ , hexane: ethyl acetate, 3: 2) was performed to obtain 30 mg (38%) of compound 13c in solid form.

m.p. > 133 ° C .;

¹ H NMR (300 MHz, CDCl ₃ ) δ 9.63 (s, 2H; CHO), 9.58 (s, 2H; CHO), 7.55-7.51 (2d, 8H, J = 3.9 Hz; FuH), 7.45 (s, 2H ThH), 7.27 (s, 2H; C = CH);

¹³ C NMR (75 MHz, CDCl ₃ ) δ 177.2 (d), 152.8, 138.7, 134.9, 132.9, 130.9, 130.4, 128.8, 128.0, 121.2, 118.4, 118.0, 101.2, 96.3, 93.1, 87.5, 85.8;

MS (FAB, m / z) 608.9 (M ++ H);

UV (CHCl ₃ ): λ max (ε 10 ⁻⁵ ) = 516 (1.4);

Elemental anal. Calcd. for C ₃₆ H ₁₆ O ₈ S ₁ : C, 71.05;

H, 2.65. Found: C, 71.28;

H, 2.68.                     

(1-11) fluorescent material 13d

To a solution of compound 11 (80.2 mg, 0.151 mmol) and 5-bromo-2-thiophenecarboxaldehyde (0.18 mL, 1.51 mmol) dissolved in Et ₃ N / MeOH (11.3 mL / 3.8 mL) (PPh ₃ ) ₂ PdCl ₂ (21 mg, 0.0299 mmol) and CuI (3 mg, 0.0157 mmol) were added. The mixture was stirred at 45-50 ° C. for 4 hours. The mixture was stirred in vacuo and the residue was subjected to silica gel column chromatography using hexane: ethyl acetate (1: 1) as the eluent to obtain Compound 13d (59.8 mg, 59%). Got it.

m.p. > 88 ° C .;

¹ H NMR (300 MHz, CDCl ₃ ) δ 9.87 (s, 2H; CHO), 9.78 (s, 2H; CHO), 7.67 (d, 2H, J = 3.9 Hz; ThH), 7.47 (d, 2H, J = 3.9 Hz; ThH, 7.40 (br d, 4H; ThH), 7.34 (d, 2H, J = 3.9 Hz; ThH), 7.25 (s, 2H; C = CH);

¹³ C NMR (75 MHz, CDCl ₃ ) δ 182.3, 182.2, 145.1, 144.5, 142.8, 138.0, 135.9, 135.7, 133.2, 132.5, 131.7, 131.1, 102.0, 100.4, 95.9, 94.6, 91.3;

MS (FAB, m / z) 672.9 (M ++ H);

UV (CHCl ₃ ): λ max (ε × 10 ⁻⁵ ) = 524 (4.0);

Elemental anal. Calcd. for C ₃₆ H ₁₆ O ₄ S ₅ : C, 64.26;

H, 2.40. Found: C, 63.89;                     

H, 2.27.

(1-12) fluorescent substance 13e

To a solution of Compound 11 (62.4 mg, 0.12 mmol) and 4-bromopyridine hydrochloride (186 mg, 0.956 mmol) dissolved in Et ₃ N / MeOH (9 mL / 3 mL) (PPh ₃ ) ₂ PdCl ₂ (17 mg, 0.0242 mmol) and CuI (2 mg, 0.0105 mmol) were added. The mixture was stirred at 45-50 ° C. for 10 hours. After evaporation of the mixture in vacuo, the residue was purified by silica gel column chromatography using ethyl acetate: methyl alcohol (10: 1) as the eluent, and the compound 13e (38.3 mg, 59%).

m.p. 246 to 249 ° C;

¹ H NMR (300 MHz, CDCl ₃ ) δ 8.49 (d, 4H, J = 4.7 Hz; PyH), 8.32 (d, 4H, J = 4.9 Hz; PyH), 7.35 (s, 2H; ThH), 7.29 ( s, 2H; C = CH), 7.26 (d, 2H, J = 5.7 Hz; PyH), 7.25 (d, 2H, J = 5.6 Hz; PyH);

¹³ C NMR (75 MHz, CDCl ₃ ) δ 145.9 (d), 142.3, 138.7, 132.3, 130.4, 129.7, 125.2, 124.7, 100.2, 95.0, 92.1, 91.8, 90.6;

MS (FAB, m / z) 540.0 (M &lt; + &gt;);                     

UV (CHCl ₃ ): λ max (ε 10 ⁻⁵ ) = 522 (1.1);

Elemental anal. Calcd. for C ₃₆ H ₂₀ N ₄ S ₁ : C, 79.98;

H, 3.73; N, 10.36. Found: C, 79.78;

H, 3.85; N, 10.21.

Example 2 Photophysical Analysis

In order to investigate the photophysical properties of the phosphors 12a to 13e and the intermediate compounds 10 to 11 of the present invention prepared above, the fluorescence quantum yields (Φ _F ) of the phosphors were determined by quinine sulfate ( quinine sulfate in 1.0 NH ₂ SO ₄ ), 9,10-diphenylanthracene (9,10-diphenylanthracenc in EtOH) and fluorescein (fluorescein in 0.1 N NaOH) were determined on CHCl ₃ using standard (Parker, CA, In Photoluminescence of Solutions, Elsevier, Amsterdam, 1968). Specifically, the absorbance of the fluorescent material synthesized in Example 1 was measured at 366 nm (or 436 nm) on a 1 × 10 ^-5 M CHCl ₃ solution, and emitted at 366 nm (or 436 nm). The area of the emission curve was measured. In this same manner, the absorption and emission curve areas of quinine sulfate and 9,10-diphenylanthracene at 366 nm were measured and then substituted into Equation 1 to determine the quantum yield of the new fluorescent material. At this time, fluorescein used values at 436 nm.

Φstd: quantum yield of standard

I: Area of Integrated Emission Curve

A: Absorbance of the sample at the excitation wavelength

n: refractive index

compound λ _abs / nm ^a λ _em / nm ^b Φ _F ^c Φ _F ^d Φ _F ^e τ _S ^f 10 412 426,463 0.01 0.01 0.03 0.6 ± 0.1 12a 416 475,506 0.19 0.21 0.35 1.2 ± 0.2 12b 438 498,532 0.29 0.32 0.25 1.6 ± 0.2 12c 450 518,551 0.10 0.11 0.16 0.6 ± 0.1 12d 456 533,566 0.08 0.08 0.16 0.8 ± 0.1 12e ^g 420 472,502 n.d. n.d. n.d. n.d. 11 458 475,503 0.01 0.01 0.01 0.3 ± 0.1 13a 468 528,561 0.09 0.09 0.08 0.4 ± 0.2 13b 486 550,587 0.03 0.03 0.07 0.7 ± 0.2 13c 516 577,618 0.01 0.01 0.03 0.4 ± 0.1 13d 524 595,628 0.01 0.01 0.03 0.5 ± 0.1 13e ^g 522 587,612 n.d. n.d. n.d. n.d. a: Only the longest absorption maximum is shown. b: emission maximum wavelength excited at the absorption maximum. c: Quantum efficiency with quinine sulfate in 1.0 NH ₂ SO ₄ as standard, λ _ex = 366 nm. d: quantum efficiency with 9,10-diphenylanthracene in EtOH as standard, λ _ex = 366 nm. e: quantum efficiency with fluorescein in 0.1 N NaOH as standard, λ _ex = 436 nm. f: half life of the excited state at the emission maximum. g: quantum yield is too low to measure.

As a result, as shown in Table 1 , the fluorescent materials 12a and 12b have a medium quantum yield and the longest fluorescence half-life (τ _S ) among all the fluorescent materials, where A in Formula 1 is a benzene ring, When B is benzene or thiophene, it shows that the photophysical properties of the fluorescent material are excellent and provides information on the influence of substituent properties and the photophysical properties of the fluorescent material for future fluorescent material development.

Example 3 Emission Spectrum Analysis

To obtain a normalized emission spectra of the phosphors of the present invention, first dilute each phosphor with 1.0 x 10 ^-5 M CHCl ₃ solution and then use the CHCl ₃ solution as a control (blank) Absorption wavelength (λ _abs ) was measured. The emission spectra appearing when excited at this wavelength were normalized to obtain a standardized emission spectra of each phosphor (Parker CA, In Photoluminescence of solution; Elsevier; Amsterdam, 1968).

As a result, in the UV-visible absorption spectra, the absorption maximum represented by the π-π * transition of the phosphor showed a significantly dependent pattern depending on the central unit of the molecules ( FIGS. 1A and 1B). ). Specifically, when the maximum absorption of the fluorescent materials 13a to 13c including the thiophene nuclei and the maximum absorption of the fluorescent materials 12a to 12e including the benzene nucleus were compared, a shift to the substantially red zone was observed. Fluorescence spectra of all phosphors showed two strong emission bands in the visible region. Emission maximums were also different depending on the aromatic nucleus of the phosphor, varying from indigo to reddish orange region ( FIG. 1C ). Fluorophore 12a and 13e of the present invention as compared to a less bonded intermediate compounds 10 and 11, and showed the large Stoke movement (Stokes shift) from about 50 to 110 nm.

As described above, the novel fluorescent materials according to the present invention exhibit emission maximums in various ranges from indigo blue to reddish orange depending on the structure composed of aromatic nuclei and surrounding residues, and are highly tuned in the field of electrons and photons because the quantum yield is very high. It can be usefully used as possible fluorescent material.

Claims (6)

Fluorescent material represented by the formula <Formula 1>

The method of claim 1, Fluorescent material, characterized in that selected from the compounds of the following structural formula:

,

,

,

,

,

,

,

,

And

A process for preparing a compound wherein B is phenyl in Formula 1 of claim 1 comprising reacting phenylacetylene with dibromo alkenes of Formula 2 in the presence of (PPh ₃ ) ₂ PdCl ₂ , CuI and Et ₃ N / alcohol solvents : <Formula 2>

Wherein A is as defined in claim 1. (PPh ₃ ) ₂ PdCl ₂ , wherein CuX (where X is Cl or I) and Et ₃ N / alcohol solvent, reacted with dibromo alkenes of Formula 2 and trimethylsilylacetylene to obtain a compound of Formula 3 B in Formula 1 of claim 1 comprising reacting with KF and bromothiophene in the presence of (PPh ₃ ) ₂ PdCl ₂ , CuX and Et ₂ NH / alcohol solvents

Process for preparing phosphorus compound: <Formula 2>

<Formula 3>

Wherein A is as defined in claim 1. (PPh ₃ ) ₂ PdCl ₂ , wherein CuX (where X is Cl or I) and Et ₃ N / alcohol solvent, reacted with dibromo alkenes of Formula 2 and trimethylsilylacetylene to obtain a compound of Formula 3 B in Formula 1 of claim 1 comprising reacting with KF and arylbromide in the presence of (PPh ₃ ) ₂ PdCl ₂ , CuX and Et ₃ N / alcohol solvents

Process for preparing phosphorus compound: <Formula 2>

<Formula 3>

Wherein A is as defined in claim 1. delete

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