JP2001247577A - Fullerene-carborane rigid rod hybrid compound and method of synthesizing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a compound suitable as a nonlinear optical material exhibiting great second harmonic generation(SHG). SOLUTION: This fullerene-carborane rigid rod hybrid compound comprises a carborane connected to a fullerene by a conjugated cross-linking aromatic group. The carborane is represented by the following chemical formula (m-CB) or the following chemical formula (p-CB) and the fullerene is C60 represented by the following chemical formula. The conjugated cross-linking aromatic group is characterized in that the group is represented by the following chemical formula (BA-1).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a fullerene-carborane hybrid material as a nonlinear material and a method for synthesizing the same.

[0002]

BACKGROUND OF THE INVENTION Electrical-to-optical signal conversion is not sufficient in the development of efficient optical telecommunications networks, but second-order nonlinear optical materials (NLO) have gained attention because of their direct applicability. I have. In this regard, Nonlinear Optic
cal Effects in Molecules and Polymers (Prasad, PN; W
illliams, DJ, Wiley, New York, 1991) and Nonlinear
Optical Properties of Organic Materials (Prasad,
P., Plenum, New York, 1991). To date, in order to obtain excellent hyperpolarizability (β), we find both the optimal combination of donor and acceptor (DA) and the optimal length of the conjugate bond between D and A (Eg, J. Am. Chem. Soc. 1993, 115, 30
06 (Marder, SR; Gorman, CB; Tiemann, BG; Cheng, L.-
T) and Science 1991, 252, 103 (Marder, SR; Beratan,
DN; Cheng, L.-T)).

[0003] For many years orthocarborane has been known to be an electron-deficient cluster with high polarizability [sigma] aromaticity (J. Mater. Chem. 1993, 3 (2), 139 (Murphy, D. .
M .; Mingos, DMP; Haggitt, JL; Powell, HR; Westcot
t, SA; Marder, TB; Taylor, NJ; Kanis, DR). Although carborane (A) containing a certain kind of electron donor (D) group has already been synthesized, its hyperpolarizability is not sufficient (J. Mater. Chem. 1993, 3, 67 (Murphy, DM; Forward) , J.
M.; Mingos, DMP)).

[0004] More recently, fullerenes have been recognized as electron-withdrawing carbon clusters having high delocalized π electrons (Chem. Rev. 1998, 98, 2527 (Marti
n, N .; Sanchez, L .; Illescas, B .; Perez, I.)). actually,
Although fullerenes (A) containing electron donor (D) moieties have been reported, no studies have been made on the nonlinear optical properties of these compounds (J. Chem. Rev. 1994, 94, 1).
95 (Kanis, DR; Ratner, MA; Marks, TJ)).

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a compound suitable as a nonlinear optical material exhibiting large second harmonic generation (SHG).

Another object of the present invention is to provide a method for synthesizing a compound suitable as a nonlinear optical material exhibiting large second harmonic generation.

[0007]

In order to solve the above-mentioned problems, the present invention provides a fullerene-carborane rigid rod hybrid compound in which carborane and fullerene are linked by a conjugated bridged aromatic group, wherein the carborane is The following chemical formula (m-CB) or the following chemical formula (p-
CB), wherein the fullerene is C ₆₀ represented by the following chemical formula, and the conjugated cross-linked aromatic group is represented by the following chemical formula (B
A fullerene-carborane rigid rod hybrid compound represented by A-1) is provided.

[0008]

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Further, the present invention provides a method of reacting 1- (4-bromophenyl) -1,7-carborane with trimethyliodine to obtain 1- (4-bromophenyl) -7-methyl-1,
Step of obtaining 7-carborane, reacting 1- (4-bromophenyl) -7-methyl-1,7-carborane with trimethylsilylacetylene to obtain 1- (4- (trimethylsilylethynyl) phenyl) -7-methyl- 1,7-
A step of obtaining carborane, deprotecting the 1- (4- (trimethylsilylethynyl) phenyl) -7-methyl-1,7-carborane to give 1- (4-ethynylphenyl)-
Obtaining 7-methyl-1,7-carborane, and 1
Lithium acetylide of-(4-ethynylphenyl) -7-methyl-1,7-carborane was obtained and reacted with fullerene to give 1-hydro-2- [1- (4-ethynylphenyl) -7-methyl [1,1,7-carborane] Fullerene is provided, and a method for synthesizing a fullerene-carborane rigid rod hybrid compound is provided.

Further, the present invention provides a reaction of 1- (4-bromophenyl) -1,12-carborane with trimethyliodine to form 1- (4-bromophenyl) -12-methyl-
A step of obtaining 1,12-carborane, reacting the 1- (4-bromophenyl) -12-methyl-1,12-carborane with trimethylsilylacetylene to obtain 1- (4-
Obtaining (trimethylsilylethynyl) phenyl) -12-methyl-1,12-carborane;
Deprotecting (trimethylsilylethynyl) phenyl) -12-methyl-1,12-carborane to obtain 1- (4-ethynylphenyl) -12-methyl-1,12-carborane; -Ethynylphenyl)
Lithium acetylide of -12-methyl-1,12-carborane was obtained and reacted with fullerene to give 1-hydro-2- [1- (4-ethynylphenyl) -12-methyl-1,12-carborane]. Provided is a method for synthesizing a fullerene-carborane rigid rod hybrid compound, which comprises a step of obtaining fullerene.

Hereinafter, the present invention will be described in detail.

The present inventors have found that an unpredictable large β value can be obtained by linking an apparently attractive carborane and fullerene via an ethynyl π system. Reached. The present invention can provide a guideline when the AA system is a promising combination for obtaining high hyperpolarizability.

The fullerene-carborane rigid rod hybrid compound of the present invention is represented by the following chemical formula.

[0014]

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The compound 5a of the present invention can be synthesized by the following procedure.

[0016]

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First, meta- which is compound 1a in THF
To a mixture of carborane derivative (1 eq) and MeI (1.1 eq) was added ⁿ BuLi (1.05 eq) to give compound 2a. Compound 1a as a raw material was obtained from J. Organomet.
Chem. 1993, 19 (Coult, R; Fox, MA; Gill, WR; Herbertso
n, PL; Macbride, JAH; Wade, K.).

[0018] Note that, when added to MeI after adding ⁿ BuLi to a THF solution of compound 1a since the yield of the compound 2a becomes very low, ⁿ BuLi, a mixture of the compound 1a and MeI It is desirable to add In the present invention, compound 2a can be obtained in a yield of 79%.

Next, a THF solution of the compound 2a is prepared, and a catalytic amount of Pd (PPh ₃ ) ₄ (2
mol3), Cul (4 mol%) and trimethylsilylacetylene (1.05 eq) in the presence of trimethylamine (1.5 eq) to give compound 3a.

Thereafter, compound 4a is obtained by deprotection of compound 3a with potassium fluoride. Compound 4a 79%
In a yield of

The compounds 5a of the present invention, with the lithium acetylide of BuLi processed and compound 4a (1 eq) of compound 4a (1 eq), this by condensing a C ₆₀ was a toluene solution, It can be synthesized with a yield of 60%.

Compound 5b can be synthesized according to the following procedure.

[0023]

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Specifically, compound 5b can be obtained by the same procedure as described above except that a para-carborane derivative is used as a starting material.

The structures of the hybrid compounds of the present invention, Compounds 5a and 5b, are ¹ H and ¹³ C NMR,
It can be specified by CV and FAB ⁺ .

[0026]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to Synthesis Examples of the compounds of the present invention and specific examples of the analysis results.

The compounds were analyzed by the following method.
The fluorescence spectrum and the UV-visible spectrum were measured at F-45.
00 spectrofluorometer (Hitachi) and U-3000UV
The analysis was performed using a visible spectrometer (manufactured by Hitachi). HR
The S measurement was performed using a q-switch Nd: YAG laser (Specron LS-412, fwhm: 6 nm) as an incident light beam. Basic light intensity (λ = 1064 nm,
I (ω)) was changed by rotating a half-wave plate provided between two polarizing plates. HRS signal, I
(2ω) was detected as a function of I (ω) by a photomultiplier (Model XP2020Q, manufactured by Philips). The basic incident light intensity and the HRS optical signal are
The signals were supplied to two gate integrators (Stanford Research System, model SR250), and the output signals from the gate integrators were AD-converted and analyzed by a personal computer.

Example 1 Synthesis of Compound 5a Synthesis of Compound 1a Meta-carborane (2.16 g, 1
5 mol) and anhydrous THF (20 ml).
For 15 minutes. Subsequently, an n-butyllithium hexane solution (1.50 M, 11 ml, 16.5 mmol)
Was slowly added dropwise and stirred at room temperature for 1 hour. afterwards,
A copper (I) -carborane solution was prepared by adding CuI (4.4 g, 23.1 mmol), adding pyridine (9 ml) for 30 minutes, and further stirring for 10 minutes at room temperature.

To the resulting solution was added p-bromoiodobenzene (4.46 g, 15.75 mmol),
Reflux at C for 5 days. After confirming by GC-MS that most of the raw material meta-carborane was consumed, the solvent was distilled off under reduced pressure, and the crude product was separated from H ₂ O / Et ₂ O (20 ml).
/ 60ml). The organic layer was dried over MgSO ₄ , concentrated, and sublimated (120 to 150 ° C./0.5 mmH
g) to give compound 1a in 31% yield.

¹ H NMR spectrum and ¹³ C NMR spectrum of the obtained compound 1a are shown in the graphs of FIGS. 1 and 2, respectively, and the characteristics are summarized below.

¹ H NMR (300 MHz, CD ₃ COCD ₃ ): δ 3.73 (s, 1 H), 7.43 (d, 2 H), 7.52 (d, 2 H) ¹³ C NMR (75.45 MHz, CD ₃ COCD ₃ ): δ 57.09, 130.58, 132.49 MS m / z: 299 (M ⁺ ) From the above analysis results, compound 1a obtained in this synthesis example
Is 1- (4-bromophenyl) represented by the following chemical formula:
It was identified as -1,7-carborane.

[0032]

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Synthesis of (Compound 2a) 1- (4-bromophenyl)-obtained in the above synthesis example
1,7-carborane (1.38 g, 4.62 mmol)
And CH ₃ I (286 μL, 4.67 mmol) were added to anhydrous THF (50 ml).
Stirred at 8 ° C. for 1.5 hours. N was added to the obtained THF solution.
-Butyl lithium hexane solution (1.50 M, 3.06
ml, 4.62 mmol) was slowly added dropwise with a syringe pump, and reacted at -78 ° C overnight.

Thereafter, the solvent was distilled off under reduced pressure, and the crude product was treated with H
Extracted with ₂ O / Et ₂ O (20 ml / 60 ml). The organic layer was dried over MgSO ₄ , concentrated, and purified by silica gel chromatography (hexane, Rf = 0.62) to give compound 2a in 79% yield.

The ¹ H NMR spectrum and ¹³ C NMR spectrum of the obtained compound 2a are shown in FIGS. 3 and 4, respectively, and the characteristics are summarized below.

[0036] ^{IR (KBr): 2594,1489,1011,732cm -1 1} H NMR (300MHz, CD 3 COCD 3): δ 1.82 (s, 3H), 7.42 (m, 2H), 7. 50 (m, 2H) ¹³ C NMR (75.45 MHz, CD ₃ COCD ₃ ): δ 24.56, 123.50, 130.20, 132.15 134.86 MS m / z: 313 (M ⁺ ) HRMS : Actual measured value of B ₁₀ C ₉ H ₁₇ Br 316.1422 calculated value 316.1425 From the above analysis results, compound 2a obtained in this synthesis example
Is 1- (4-bromophenyl) represented by the following chemical formula:
It was identified as -7-methyl-1,7-carborane.

[0037]

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Synthesis of (Compound 4a) 1- (4-bromophenyl)-obtained in the above synthesis example
7-methyl-1,7-carborane (1.17 g, 2.3
7 mmol), Pd (PPh ₃ ) ₄ (430 mg, 0.3
7 mmol), CuI (97 mg, 0.52 mmol)
l), and triethylamine (0.52 ml, 3.7
mmol) was added to anhydrous THF (50 ml), and the mixture was stirred at 0 ° C for 30 minutes under an argon atmosphere. The obtained THF
To the solution was added trimethylsilylacetylene (0.78 ml,
(5.55 mmol), and the mixture was further stirred at 0 ° C for 2 hours, and then refluxed at 100 ° C for 1 day.

After confirming the consumption of the starting compound 2a by GC-MS, the solvent was distilled off under reduced pressure and KF (591.4 mg,
10.4 mmol), KOH (50 mg, 0.8 mmol)
l), MeOH (50 ml) was newly added, and the mixture was stirred at room temperature for 1 hour. Thereafter, the solvent was distilled off under reduced pressure, and
Extracted with ₂ O / Et ₂ O (20 ml / 60 ml). The organic layer was dried over MgSO ₄ , concentrated, and purified by silica gel column chromatography using hexane as a developing solvent to obtain Compound 4a at a yield of 79%.

The ¹ H NMR spectrum and ¹³ C NMR spectrum of the obtained compound 4a are shown in FIG. 5 and FIG.
And their characteristics are summarized below.

[0041] ^{IR (KBr): 3304,2600,874,856cm -1 1} H NMR (300MHz, CD 3 COCD 3): δ 1.83 (s, 3H), 3.75 (s, 1H), 7. 43-7.51 (m, 2H) ¹³ C NMR (75.45 MHz, CD ₃ COCD ₃ ): δ 24.82, 80.93, 82.93, 128.78, 129.41 132.85, 136. 24 MS m / z: 258 (M ⁺ ) HRMS: measured value of B ₁₀ C ₁₁ H ₁₈ 260.2337 calculated value 260.2339 From the above analysis results, compound 4a obtained in this Synthesis Example
Was identified as 1- (4-ethynylphenyl) -7-methyl-1,7-carborane represented by the following chemical formula.

[0042]

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This compound was synthesized by deprotecting a compound represented by the following chemical formula.

[0044]

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Synthesis of (Compound 5a) 1- (4-ethynylphenyl) obtained in the above synthesis example
-7-methyl-1,7-carborane (51.6 mg,
0.2 mmol) in anhydrous THF solution, n-butyllithium hexane solution (1.50 M, 0.13 ml, 0.23
mmol) was added at 0 ° C. under an argon atmosphere, followed by stirring at room temperature for 1 hour. This was designated as solution A.

[0046] Under an argon atmosphere, C ₆₀ at 35 ° C. (72
(mg, 0.1 mmol) in anhydrous toluene. After the reaction solution was stirred at 35 ° C. overnight, CF ₃ COOH (2 ml) was added thereto for further 2 hours.
After stirring for an hour, the solvent was distilled off under reduced pressure. The obtained crude product was dissolved in CHCI ₃ , and the insolubles were filtered using a filter paper, and then CHCI ₃ was distilled off under reduced pressure. The crude product was further washed with a small amount of hexane using a glass filter to remove unreacted compound 4a. Finally, the product was purified by flash column chromatography (hexane) to give a yield of 60.
% Yielded compound 5a.

The 1H NMR spectrum of the obtained compound 5a is shown in the graph of FIG. 7, and its characteristics are summarized below.

IR (KBr): 2594, 1717, 1663, 1506, 1456, 1429, 1182, 1090, 1067, 980 cm ^{−1 1} H NMR (CS ₂ / CD ₂ Cl ₂ ): δ 2.36 (s, 3H) ), 7.17-7.27 (m, 5H) Mass spectrum (FAB ⁺ ) m / z: 977 (M ⁺ -H); 817.0 (M ⁺ -(1-Me-1,7-C _{2) B 10 H 11); 744 (} M + - (1-Me, 7-Ph-1,7-C 2 B 10 H 10); 721 (C60H); 720 (C60); 258 (1- (CC-Ph ), 7-Me-1,7- ( C 2 B 10 H 10)) 234 (1-Me, 7-Ph, 1,7-C 2 B 10 H 10); 158 (1-Me-1,7 -C ₂ B ₁₀ H ₁₀ ) Based on the above analysis results, compound 5a obtained in this synthesis example
Is 1-hydro-2- [1- (4
-Ethynylphenyl) -7-methyl-1,7-carborane] fullerene.

[0049]

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(Example 2: Compound 5b) Synthesis of (Compound 1b) Para-carborane (2.16 g, 1
5 mol) and anhydrous THF (20 ml).
For 15 minutes. Subsequently, an n-butyllithium hexane solution (1.50 M, 11 ml, 16.5 mmol)
Was slowly added dropwise and stirred at room temperature for 1 hour. afterwards,
A copper (I) -carborane solution was prepared by adding CuI (4.4 g, 23.1 mmol), adding pyridine (9 ml) for 30 minutes, and further stirring for 10 minutes at room temperature.

To the resulting solution was added p-bromoiodobenzene (4.46 g, 15.75 mmol), and 100
Reflux at C for 5 days. After confirming by GC-MS that most of the raw material para-carborane was consumed, the solvent was distilled off under reduced pressure, and the crude product was washed with H ₂ O / Et ₂ O (20 ml).
/ 60ml). The organic layer was dried over MgSO ₄ , concentrated, and purified by sublimation (125 ° C./0.5 mmHg) to obtain Compound 1b in a yield of 36%.

The ¹ H NMR spectrum and ¹³ C NMR spectrum of the obtained compound 1b are shown in the graphs of FIGS. 8 and 9, respectively, and the characteristics are summarized below.

¹ H NMR (300 MHz, CD ₃ COCD ₃ ): δ 3.73 (s, 1 H), 7.20 (m, 2 H), 7.44 (m, 2 H) ¹³ C NMR (75.45 MHz, CD ₃ COCD ₃ ): δ 57.09, 130.58, 132.49 MS m / z: 299 (M ⁺ ) From the above analysis results, compound 1b obtained in this synthesis example
Is 1- (4-bromophenyl) represented by the following chemical formula:
It was identified as -1,12-carborane.

[0054]

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Synthesis of (Compound 2b) 1- (4-bromophenyl)-obtained in the above synthesis example
1,12-carborane (867 mg, 2.9 mmol)
And CH ₃ I (195 μL, 3.2 mmol) in anhydrous T
In addition to HE (50 ml), -78
Stirred at 1.5 ° C. for 1.5 hours. N- is added to the obtained THE solution.
Butyl lithium hexane solution (1.50 M, 1.93 m
1,2.9 mmol) was slowly added dropwise with a syringe pump, and the mixture was reacted at -78 ° C overnight.

Thereafter, the solvent was distilled off under reduced pressure, and the crude product was treated with H
Extracted with ₂ O / Et ₂ O (20 ml / 60 ml). The organic layer was dried over MgSO ₄ , concentrated, and purified by silica gel chromatography (hexane, Rf = 0.60) to give compound 2b in 72% yield.

The ¹ H NMR spectrum and ¹³ C NMR spectrum of the obtained compound 2b are shown in FIG. 10 and FIG.
1 and their characteristics are summarized below.

IR (KBr): 2603, 1491, 1394, 1342, 1123, 880 cm ^{−1 1} H NMR (300 MHz, CD ₃ COCD ₃ ): δ 1.46 (s, 3H), 7.14 (d, 2H) ), 7.38 (d, 2H) ¹³ C NMR (75.45 MHz, CD ₃ COCD ₃ ): δ 25.81, 129.87, 132.12 MS m / z: 313 (M ⁺ ) HRMS: B ₁₀ Actual value of C ₉ H ₁₇ Br 316.1440 Calculated value 316.1425 From the above analysis results, compound 2b obtained in this synthesis example
Is 1- (4-bromophenyl) represented by the following chemical formula:
It was identified as -12-methyl-1,12-carborane.

[0059]

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Synthesis of (Compound 4b) 1- (4-bromophenyl)-obtained in the above synthesis example
12-methyl-1,12-carborane (1.17 g,
2.37 mmol), Pd (PPh ₃ ) ₄ (430 mg,
0.37 mmol), CuI (97 mg, 0.52 mm)
ol), and triethylamine (0.52 ml, 3.
7 mmol), anhydrous THF (50 ml) was added, and the mixture was stirred at 0 ° C for 30 minutes under an argon atmosphere. Subsequently, trimethylsilylacetylene (0.78 ml, 5.55 mm
ol) and further stirred at 0 ° C. for 2 hours.
Refluxed at 0 ° C. for 1 day.

After confirming the consumption of the starting compound 2b by GC-MS, the solvent was distilled off under reduced pressure and KF (591.4 mg,
10.4 mmol), KOH (50 mg, 0.8 mmol)
l), MeOH (50 ml) was newly added, and the mixture was stirred at room temperature for 1 hour. Thereafter, the solvent was distilled off under reduced pressure, and
Extracted with ₂ O / Et ₂ O (20 ml / 60 ml). The organic layer was dried over MgSO ₄ , concentrated, and purified by silica gel column chromatography using hexane as a developing solvent to obtain Compound 4b in a yield of 79%.

The ¹ H NMR spectrum and ¹³ C NMR spectrum of the obtained compound 4b are shown in the graphs of FIGS. 12 and 13, respectively, and the characteristics are summarized below.

[0063] ^{IR (KBr): 3302,2602,1067,856,816cm -1 1} H NMR (300MHz, CD 3 COCD 3): δ 1.48 (s, 3H), 3.66 (s, 1H), 7.20-7.35 (m, 4H) ¹³ C NMR (75.45 MHz, CD ₃ COCD ₃ ): δ 25.83, 80.55, 82.93, 123.49, 127.99 128.95, 132.50 MS m / z: 258 (M ⁺ ) HRMS: Observed value of B ₁₀ C ₁₁ H ₁₈ 260.2343 Calculated value 260.2339 From the above analysis results, compound 4b obtained in this synthesis example
Was identified as 1- (4-ethynylphenyl) -12-methyl-1,12-carborane represented by the following chemical formula.

[0064]

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This compound was synthesized by deprotecting a compound represented by the following chemical formula.

[0066]

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Synthesis of (Compound 5b) 1- (4-ethynylphenyl) obtained in the above synthesis example
-12-methyl-1,12-carborane (51.6 m
g, 0.2 mmol) in anhydrous THF solution of n-butyllithium in hexane (1.50 M, 0.13 ml, 0.1 g).
2 mmol) at 0 ° C. under an argon atmosphere.
Stirred at room temperature for 1 hour. This was designated as solution A.

[0068] Under an argon atmosphere, C ₆₀ at 35 ° C. (72
(mg, 0.1 mmol) in anhydrous toluene. After the reaction solution was stirred at 35 ° C. overnight, CF ₃ COOH (2 ml) was added thereto for further 2 hours.
After stirring for an hour, the solvent was distilled off under reduced pressure. The obtained crude product was dissolved in CHCI ₃ , and the insolubles were filtered using a filter paper, and then CHCI ₃ was distilled off under reduced pressure. Further, the crude product was washed with a small amount of hexane using a glass filter to remove unreacted compound 4b. This was purified by flash column chromatography (hexane) to give a yield of 50.
% Yielded compound 5b.

The ¹ H NMR spectrum and ¹³ C NMR spectrum of the obtained compound 5b are shown in FIGS.
5 are shown in the respective graphs, and their characteristics are summarized below.

[0070] IR (KBr): 2588,1719,1701,1560,1541,1508,1458, 1057cm -1 1 H NMR (CDCl 3 / CS 2): δ 1.58 (s, 3H), 7.21- 7.37 (m, 5H) 13 C NMR (CDCl ₃ / CS ₂ ): δ 25.66, 78.71, 82.84, 109.99, 112.47 118.63, 120.05, 122.42, 124.16 127.23, 127.99, 128.20, 128.67 129.24, 130.19, 131.05, 131.32 131.72, 132.68, 133.97, 136.46 139. 11, 140.02, 140.71, 143.00 145.51, 147.01, 147.63, 149.71 150.46, 151.30 Mass spec Torr ^{(FAB +) m / z:} 977 (M + -H); 817.0 (M + - (1-Me-1,12-C 2 B 10 H 11); 744 (M + - (1-Me , 12-Ph-1,12-C 2 B 10 H 10); 721 (C60H) 720 (C60); 258 (1- (CC-Ph), 12-Me-1,12-C 2 B 10 H 10 )) 234 (1-Me, 12-Ph, 1,12-C ₂ B ₁₀ H ₁₀ ); 158 (1-Me-1,12-C ₂ B ₁₀ H ₁₀ ) Compound 5b obtained from
Is 1-hydro-2- [1- (4
-Ethynylphenyl) -12-methyl-1,12-carborane] fullerene.

[0071]

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[0072] The cyclic voltaic Bruno grams of the resulting compound 5a and C ₆₀ shown in the graph of FIG. 16. In the graph, curve a represents the cyclic voltammogram of compound 5a, which was used at 4 × 10 ⁻³ M in ortho-dichlorobenzene. Curve b is C ₆₀
It represents a cyclic Volta Roh grams, C ₆₀ ortho -
Used as 2.5 × 10 ⁻³ M in dichlorobenzene.

The conditions are as follows.

[0074] supporting electrolyte: 0.1M ⁿ Bu ₄ NClO ₄ working electrode: glassy carbon counter electrode: Pt line reference electrolyte: in acetonitrile Ag / 0.01 N A
gNO ₃ containing 0.1 M ⁿ Bu ₄ ClO ₄ (E _1/2 (ferrocene / ferrocenium) = 180 V) Scanning speed: 100 mVs ⁻¹ Further, FIG. 17, FIG. 18 and FIG.
b, Compound 6 shown below (TMS ethynyl-1,2-
2 shows cyclic voltammograms of dihydro- [60] fullerene) and compound 7 (ethynyl analog) shown below, respectively. Compound 5b was used at 4 × 10 ⁻³ M in ortho-dichlorobenzene and compound 6 and compound 7 were each used at 5 × 10 ⁻³ M in ortho-dichlorobenzene.
Used as 10 ⁻³ M and 3 × 10 ⁻³ M. The conditions are the same as described above.

[0075]

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Table 1 below summarizes the E ₁ ^red / E ₁ ^ox , E ^ox and β values for compounds 5a, 5b, 6 and 7. For simplicity, only E ₁ ^red / E ₁ ^ox values are shown in Table 1, but three pseudo-reversible reduction / oxidation peaks were observed.

[0077]

[Table 1]

[0078] When discussing the electrochemical properties of the C ₆₀ end groups, one-electron oxidation of one-electron reduction (E ₁ ^red) and molecular 5a uncharged molecules 5a (E ₁ ^ox) is further charged molecules More important than reduction (E ₂ ^red and E ₃ ^red ).

Curve a (compound 5a) is similar to curve b
Under the same conditions as (C ₆₀ ), compound 6 (FIG. 18) and compound 7 (FIG. 19), three pseudo reversible reduction waves are also shown. Specifically, the curve a includes (E _red E _ox
mV; -1210: -581, -1167: -102
4, -217: -1635), and three quasi-reversible reduction waves (E _red : E _ox mV; -1103: -631) are shown in curve b (C ₆₀ ). -1
516: -1083, 1989: -1595).

-79 mV (E ^ox ) for compound 5a
The presence of an irreversible oxidation wave at corresponds to the oxidation peak of the conjugated spacer fragment. This is because compounds 6 and 7 also show oxidation peaks at -122.5 mv and -286 mv, respectively. As shown in the graph of FIG. 16, three reduction potential curve a for compound 5a is markedly shifted to a negative value than the reduction potential of the curve b for C _60. this is,
Is due to the electron-donating properties of saturated and ethynylphenyl group double bond of C _60. Therefore, compound 5
C ₆₀ skeleton of a are apparent to act as an A group, it is the same for compound 5b is seen from the graph of the results shown in Table 1 and Figure 17.

What is important here is whether the carborane skeleton functions as a donor or as a conventional attractant. As shown in Table 1, compounds 4a and 4b are not electrochemically active within the observed range, and it is not clear whether the carborane skeleton is the donor of the donor. However, the E ^ox value of compound 7 was -285 mV
Is the most negative value. This indicates that the electron density of the ethynyl group of compound 7 is larger than that of compounds 5a and 5b. Thus, the carborane end group is
Already established (Tetrahedron Lett. 1999, 40, 907
3 (Endo, T; Taoda, Y)).

The UV absorption spectra of the compounds 5a and 5b of the present invention are shown in the graphs of FIGS. 20 and 21, respectively. Compound 5a and compound 5b were used as 5 × 10 ⁻⁶ M and 1 × 10 ⁻⁶ M in chloroform, respectively.

As shown in these graphs, the absorption spectrum of compound 5a / CH ₃ Cl and the absorption spectrum of compound 5b / CH ₃ Cl in the UV visible region show a very weak absorption band at 430 nm due to the forbidden transition. 620 nm and two large absorption bands at 25
It is at 7 nm and 330 nm. In chloroform, compounds 5a and 5b are transparent in the UV-visible range and no absorption is observed.

For reference, the UV spectra of compounds 4a, 4b, 6 and 7 are shown in FIGS.
The results are shown in the graph of FIG. Compound 4a and compound 4b were prepared in chloroform at 5 × 10 ⁻⁶ M and 1 × 10 ⁻⁶ , respectively.
M, and both compounds 6 and 7 were used as 2.5 × 10 ⁻⁶ M in chloroform.

As shown in the graphs of FIGS. 22 and 23, compounds 4a and 4b are also transparent above 300 nm.

The graph of FIG. 26 shows the compound 5a of the present invention.
3 shows a fluorescence spectrum of chloroform in chloroform. As shown in the graph, the fluorescence spectrum of compound 5a in chloroform shows a broad emission band in the range of 350 to 390 nm following excitation at 257 nm and 330 nm, due to the Raman scattering of chloroform. (Fluorescence emission was measured in THF and CH ₃ CN
Among them).

In the range of the double frequency of 532 nm, no spectral absorption and / or emission is observed, and the β value can be obtained by simultaneously measuring the β coefficient of the compound 5a.

The same results as described above were obtained for the fluorescence spectrum of compound 5b in chloroform.

The graph of FIG. 27 shows the ultra Rayleigh scattering (HRS) signal of compound 5a in chloroform. This graph shows the second order dependence of the second harmonic signal intensity on the harmonic intensity, with the horizontal and vertical axes representing the fundamental intensity and the second harmonic intensity, respectively.

In the unit of 10 ¹⁴ cm ^-3 , 3
The different number densities are shown, the numbers c, d and e being 15, 60 and 150 respectively.

Based on the results shown in the graph of FIG. 27, the number density of compound 5a and the quadratic coefficient I (2ω) / I ²
(Ω) is shown in the graph of FIG.

The β value for compound 5a of the present invention is 4
It is as large as 83 × 10 ^-30 esu.

The graph of FIG. 29 shows the compound 5b of the present invention.
1 shows the HRS signal of the present invention. Here, four different number densities in a unit of 10 ¹⁴ cm ^-3 are shown, and the number densities of the curves f, g, h and i are 3.0, 1 and 2, respectively.
5, 30, and 60. The relationship between the number density and the quadratic coefficient is shown in the graph of FIG. The β value of compound 5b was 1189 × 10 ⁻³⁰ esu, and it was confirmed that the para derivative had an extremely large β value.

[0094] The graph of FIG. 31 shows the HRS signal of C _60. In the graph, the horizontal axis and the vertical axis represent the basic intensity and the second harmonic intensity, respectively, and are 2.2, 4.
Four types of number densities of 4, 22, and 44 × 10 ¹⁴ cm ⁻³ are shown.

[0095] The relation between the number density and the secondary coefficient of the C ₆₀ in chloroform at 293K in the graph of FIG. 32. Beta value of C ₆₀ is zero, which is due to the central symmetry structure of C _60.

Further, similar results for Compound 6 are shown in the graphs of FIGS. 33 and 34, and similar results for Compound 7 are shown in the graphs of FIGS. 35 and 36.
Compound 6 and Compound 7 are typical DA systems, and their β values are 87 × 10 ⁻³⁰ esu, respectively.
And 139 × 10 ⁻³⁰ esu.

The similar results for compound 4a are shown in the graphs of FIGS. 37 and 38, and the similar results for compound 4b are shown in the graphs of FIGS. 39 and 40.
FIG. 39 shows four different number densities in a unit of 10 ¹⁵ cm ^{−3, and} the number densities of the curves j, k, m, and n are 60, 150, 300, and 450. The β values of compounds 4a and 4b were 28 ×
It was 10 ^-30 esu and 48 × 10 ^-30 esu. The β value for para-nitroaniline under the same conditions was found to be 23 × 10 ⁻³⁰ .

As described above, by binding carborane, a large β value of 1189 × 10 ⁻³⁰ esu could be obtained at the maximum, and a strong electron polarization effect of the boron cluster was confirmed.

In particular, the nonlinear optical properties of the hybrid rod compound 5b of the present invention are very interesting.
Conventionally, by combining with a suitable donor to form a charge transfer complex, J. Phys.Chem. 1992, 96, 530 (Wang,
Y.;. Cheng, L.-T ) as described in, the center of symmetry of C ₆₀ was estimated to collapse. In contrast, the rod hybrid compounds 5a and 5b of the present invention show a large β value without forming a charge complex.

In the present invention, C ₆₀ and carborane can be formed by various conjugated bridged aromatic groups (thiophene, aniline).
In particular, by connecting the metallocarborane anion complex,
It is also possible to form triads.

The present invention can be applied to a third-order optical nonlinear material of a fullerene-carborane (or metallocarborane) hybrid rod.

[0102]

As described in detail above, according to the present invention,
A compound suitable as a nonlinear optical material exhibiting large second harmonic generation (SHG) is provided. Further, according to the present invention, there is provided a method for synthesizing a compound suitable as a nonlinear optical material exhibiting large second harmonic generation.

The hybrid compound of the present invention not only has a high beta value but also has a high stability, so that it can be treated in air in the same manner as a normal compound. INDUSTRIAL APPLICABILITY The present invention is most suitable as a non-linear optical material, and can be suitably used for many applications such as a wavelength conversion element, a non-linear material, and an optical disk, and has a great industrial value.

[Brief description of the drawings]

FIG. 1 is a ¹ H NMR spectrum of compound 1a.

FIG. 2 is a ¹³ C NMR spectrum of compound 1a.

FIG. 3 is a ¹ H NMR spectrum of compound 2a.

FIG. 4 is a ¹³ C NMR spectrum of compound 2a.

FIG. 5 is a ¹ H NMR spectrum of compound 4a.

FIG. 6 is a ¹³ C NMR spectrum of compound 4a.

FIG. 7 is a ¹ H NMR spectrum of compound 5a.

FIG. 8 is a ¹ H NMR spectrum of compound 1b.

FIG. 9 is a ¹³ C NMR spectrum of compound 1b.

FIG. 10 is a ¹ H NMR spectrum of compound 2b.

FIG. 11 is a ¹³ C NMR spectrum of compound 2b.

FIG. 12 is a ¹ H NMR spectrum of compound 4b.

FIG. 13 is a ¹³ C NMR spectrum of compound 4b.

FIG. 14 is a ¹ H NMR spectrum of compound 5b.

FIG. 15 is a ¹³ C NMR spectrum of compound 5b.

Cyclic Volta Bruno grams of [16] Compounds 5a and C _60.

FIG. 17 is a cyclic voltammogram of compound 5b.

FIG. 18 is a cyclic voltammogram of compound 6.

FIG. 19 is a cyclic voltammogram of compound 7.

FIG. 20 is a UV absorption spectrum of compound 5a.

FIG. 21 is a UV absorption spectrum of compound 5b.

FIG. 22 is a UV absorption spectrum of compound 4a.

FIG. 23 is a UV absorption spectrum of compound 4b.

FIG. 24 is a UV absorption spectrum of Compound 6.

FIG. 25 is a UV absorption spectrum of Compound 7.

FIG. 26 is a fluorescence spectrum diagram of compound 5a in chloroform.

FIG. 27 is a graph showing a super-Rayleigh scattering signal of compound 5a in chloroform.

FIG. 28 shows the number density and quadratic coefficient I (2ω) / of compound 5a.
FIG. 3 is a graph showing a relationship with I ² (ω).

FIG. 29 is a graph showing a super Rayleigh scattering (HRS) signal of compound 5b in chloroform.

FIG. 30: Number density of compound 5b and quadratic coefficient I (2ω) /
FIG. 3 is a graph showing a relationship with I ² (ω).

Figure 31 is a graph diagram showing the HRS signal of C _60.

Figure 32 is a graph showing the relationship between the number density and the secondary coefficient of C _60.

FIG. 33 is a graph showing the HRS signal of compound 6 in chloroform.

FIG. 34 is a graph showing the relationship between the number density of compound 6 and a quadratic coefficient.

FIG. 35 is a graph showing the HRS signal of compound 7 in chloroform.

FIG. 36 is a graph showing the relationship between the number density of compound 7 and a quadratic coefficient.

FIG. 37. HRS of compound 4a in chloroform
FIG. 3 is a graph showing a signal.

FIG. 38 is a graph showing the relationship between the number density and the quadratic coefficient of compound 4a.

FIG. 39. HRS of compound 4b in chloroform
FIG. 3 is a graph showing a signal.

FIG. 40 is a graph showing the relationship between the number density and the quadratic coefficient of compound 4b.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Ryo Hamasaki, Inventor 1-30-30 Yagiyama Honcho, Taishiro-ku, Sendai-shi, Miyagi Prefecture F-term (reference) 2K002 AB12 CA05 GA10 HA20 4H048 AA01 AA02 AB76 AB92 AC23 AC80 AC90 BD70 VA75 VB10

Claims (3)

[Claims] 1. A fullerene-carborane rigid rod hybrid compound in which carborane and fullerene are linked by a conjugated bridged aromatic group, wherein the carborane is represented by the following chemical formula (m-CB) or the following chemical formula (p-CB): Wherein the fullerene is C ₆₀ represented by the following chemical formula, and the conjugated cross-linked aromatic group is represented by the following chemical formula (BA-1). Embedded image 2. 1- (4-bromophenyl) -1,7-
Reaction of carborane with trimethyl iodine gives 1- (4
A step of obtaining -bromophenyl) -7-methyl-1,7-carborane, wherein said 1- (4-bromophenyl) -7-methyl-1,7
Reacting carborane with trimethylsilylacetylene to obtain 1- (4- (trimethylsilylethynyl) phenyl) -7-methyl-1,7-carborane; the above-mentioned 1- (4- (trimethylsilylethynyl) phenyl) -7- Deprotecting methyl-1,7-carborane,
1- (4-ethynylphenyl) -7-methyl-1,7-
Step of obtaining carborane, and lithium acetylide of 1- (4-ethynylphenyl) -7-methyl-1,7-carborane, which is reacted with fullerene to give 1-hydro-2- [1- (4- A method for synthesizing a fullerene-carborane rigid rod hybrid compound, comprising the step of obtaining [ethynylphenyl) -7-methyl-1,7-carborane] fullerene. 3. 1- (4-bromophenyl) -1,12
Reacting carborane with trimethyl iodine to form 1-
A step of obtaining (4-bromophenyl) -12-methyl-1,12-carborane; the above-mentioned 1- (4-bromophenyl) -12-methyl-1,1
Reacting 2-carborane with trimethylsilylacetylene to obtain 1- (4- (trimethylsilylethynyl) phenyl) -12-methyl-1,12-carborane; 1- (4- (trimethylsilylethynyl) phenyl) -12 Deprotection of -methyl-1,12-carborane gives 1- (4-ethynylphenyl) -12-methyl-
A step of obtaining 1,12-carborane;
-Ethynylphenyl) -12-methyl-1,12-carborane lithium acetylide was obtained and reacted with fullerene to give 1-hydro-2- [1- (4-ethynylphenyl) -12-methyl-1, [12-Carborane] A method for synthesizing a fullerene-carborane rigid rod hybrid compound, comprising a step of obtaining a fullerene.