JP3318604B2 - Fullerene-carborane rigid rod hybrid compound and method for synthesizing same - Google Patents

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. The main purpose is to provide a donor π-acceptor (D-
π-A) molecular design, the length of the π system and the donor,
The purpose is to optimize the first-order hyperpolarizability (β) by selecting the optimal acceptor. This is described in the following document. Nonlinear Optical Effectsin
Molecules and Polymers (Prasad, PN; Willliams, D.
J., Wiley, New York, 1991), J. Phys. Chem. 1991, 9
5, 10643 (Cheng, L.-T .; Tam, W .; Marder, SR; Stiegma
n, AE; Rikken, G .; Spangler, CW), J. Am. Chem. So
c. 1993, 115, 3006 (Marder, SR; Gorman, CB; Tiemann,
BG; Cheng, L.-T.), J. Chem. Soc. Chem. Comm. 1992,672
(Marder, SR; Cheng, L.-T .; Tiemann, BG), J. Am. Chem.
Soc. 1991, 113, 7568 (Stiegman, AE; Graham, E; Perr
y, KJ; Khundkar, LRPerry, JW ,; Cheng, L.-T.), JC
hem.Soc.Chem.Comm.1993, 1119 (Rao, VP; Jen, AK-y, Wo
ng, KY; Drost, KJ), Science 1991, 252, 103 (Marde
r, SR; Beratan, DN; Cheng, L.-T.), Chem.Phys.Lett.
1992,191,245 (Stahelin, M .; Burland, DM; Rice.J.
E.), and Chem. Phys. 1990, 145, 3433 (Ramasesha, S .;
Dass, PK).

[0003] For electronic high delocalization on the fullerene shell, the C ₆₀ based materials, to exhibit great nonlinear optical effects than those for π-conjugated polymer is expected. In this regard, Nonlinear Optical Properti
es of Organic Materials (Prasad, P., Plenum, New Yo
rk, 1991). Fullerene (A) bound to an electron donor (D) moiety has been widely reported (A-
D). (Chem. Rev. 1998, 98, 2527 (Martin, N .; Sanche
z, L.; Illescas, B.; Perez, I.)). At present, fullerene (AA) combined with electron acceptor (A) moiety
Has been little studied.

[0004]

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).

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

[0006]

In order to solve the above-mentioned problems, the present invention provides a fullerene-carborane rigid rod hybrid compound wherein carborane and fullerene are linked by a conjugated bridged aromatic group. provide.

Further, the present invention provides a method of reacting 1- (4-bromophenyl) -1,2-carborane with methyl iodine to form 1- (4-bromophenyl) -2-methyl-1,2-.
A step of obtaining carborane, reacting 1- (4-bromophenyl) -2-methyl-1,2-carborane with trimethylsilylacetylene to obtain 1- (4- (trimethylsilylethynyl) phenyl) -2-methyl-1, Step of obtaining 2-carborane, deprotecting the 1- (4- (trimethylsilylethynyl) phenyl) -2-methyl-1,2-carborane to obtain 1- (4-ethynylphenyl) -2
Obtaining -methyl-1,2-carborane, and the 1- (4-ethynylphenyl) -2-methyl-1,2-
A fullerene comprising a step of obtaining lithium acetylide of carborane and reacting this with fullerene to obtain 1-hydro-2- [1- (4-ethynylphenyl) -2-methyl-1,2-carborane] fullerene. A method for synthesizing a carborane rigid rod hybrid compound is provided.

Hereinafter, the present invention will be described in detail.

The present inventors have synthesized a hybrid compound considered to be an A-π-A system by covalently linking carborane to fullerene by a conjugated spacer, thereby obtaining an electronic structure of an ortho-carborane electron-deficient cluster and its higher structure. Polar σ part (J. Mater. Chem. 1993, 3 (2),
139 (Murphy, DM; Mingos, DMP; Haggitt, JL; Powell,
HR; Westcott, SA; Marder, TB; Taylor, NJ; Kani
s, DR), J. Mater. Chem. 1993, 3, 67 (Murphy, DM; Forw
ard, JM; Mingos, DMP)), exhibiting unprecedented electrochemical behavior, with fullerene as the acceptor
Carborane was found to act as a donor.

Further, this fullerene-π-carborane rigid rod hybrid compound has a high second harmonic generation (SHG) (J. Chem. Rev. 1994, 94, 195 (Kanis, DR;
Ranter, MA; Marks, TJ)) was first found by the present inventors.

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

[0012]

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This compound can be synthesized by the following procedure.

[0014]

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First, ortho- which is the compound 1 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 2. Compound 1, which is a raw material, is obtained from J. Organomet.che
m. 1993, 19 (Coult, R; Fox, MA; Gill, WR; Herbertso
n, PL; Macbride, JAH; Wade, K.).

[0016] Note that, when added to MeI after adding ⁿ BuLi to a THF solution of Compound 1, since the yield of Compound 2 becomes very low, ⁿ BuLi, a mixture of Compound 1 and MeI It is desirable to add In the present invention, compound 2 can be obtained with a yield of 87%.

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

Thereafter, compound 4 is obtained by deprotection of compound 3 with potassium fluoride. Compound 4 is obtained in a yield of 80%.

The compound 5 of the present invention is prepared from BuLi (1 equivalent)
To give a lithium acetylide of compound 4 (1 equivalent), which can be synthesized by condensing it with C ₆₀ in a toluene solution. (For example, Te
trahedron Lett. 1996, 52,4925 (Timmerman, P .; Ander
son HL; Faust, R .; Nierengarten, JF .; Habicher,
T .; Seiler, P .; Diederich, T.), J. Org. Chem. 199
4, 59,6101 (Komatsu, K .; Murata, Y .; Takimoto, N .;
Mori, S .; Sugita, N .; Wan, TS)).

The structure of Compound 5, which is a hybrid compound of the present invention, is represented by ¹ H, ¹³ C NMR, CV and E
SI ^- makes it possible to identify.

[0021]

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 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.

Synthesis of (Compound 1) KO ^t Bu (5.61 g, 50 mmol) was added to dry glyme (80 ml) and CuI (8.57) under a nitrogen atmosphere.
g, 45 mmol) at room temperature for 5 hours, pyridine (10 ml) was added, and ortho-carborane (4.26 g, 30 mmol) was further added.

The resulting mixture (copper (I) carborane solution) was stirred at 40 ° C. for 2 hours, and 4-bromoiodobenzene (8.48 g, 30 mmol) was added at once to obtain a mixture of 100 parts.
Stirred at C for 5 days. At this time, it was confirmed by GC-MS that the carborane was almost consumed.

Thereafter, the solvent was distilled off, and the crude oil was extracted with an ether / water system (120 ml ether / 40 ml water). The organic layer was separated, dried over MgSO ₄ and concentrated to give a yellow solid. Finally, recrystallization from ethanol gave white crystals (Compound 1) in 63% yield.

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

¹ H NMR (300 MHz, CD ₃ CO
CD ₃ ): δ 3.84 (s, 1H), 7.19-7.
42 (2d, 4H) ¹³ C NMR (75.45 MHz, CD ₃ COC
D ₃ ): δ 60.10, 129.17, 131.98 MS m / z: 299 (M ⁺ ) HRMS: Calculated value of C ₈ H ₁₅ B ₁₀ Br, 300.128
8 Actual measurement value 300.1330 From the above analysis results, Compound 1 obtained in this synthesis example was
1- (4-bromophenyl)-represented by the following chemical formula
It was identified as 1,2-carborane.

[0028]

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Synthesis of (Compound 2) 1- (4-bromophenyl)-obtained in the above synthesis example
1,2-carborane (2.99 g, 10 mmol);
A THF solution of a mixture with CH ₃ I (0.75 ml, 12 mmol) was prepared. ^N Bu is added to the obtained THF solution.
Li hexane solution (1.57 M, 6.7 ml, 10.
5 mmol) was slowly added dropwise at -78 ° C under a dry Ar atmosphere. The solution was left at that temperature overnight, GC-Mass
Monitored the progress of the reaction.

When the starting material has been consumed, the solvent is distilled off,
The resulting crude oil was washed with H ₂ O / Et ₂ O (20 ml / 60
ml). The organic layer was dried over MgSO ₄ and the ether was distilled off to give a yellow solid. Finally, silica gel PTLC chromatography (hexane / CH ₂ C
Purification with l ₂ = 9/1 solvent) gave 87% (2.72).
A white solid (compound 2) was obtained in the yield of g).

The ¹ H NMR spectrum, ¹³ C NMR spectrum and IR spectrum of the obtained compound 2 were
The characteristics are shown in the graphs of FIGS. 3, 4 and 5, respectively, and are summarized below.

IR (KBr): 2601, 2585, 2
^{509,1489,829,503cm -1 1 H NMR (300MHz,} CD 3 COCD 3): δ
1.80 (s, 3H), 7.70 (s, 4H) ¹³ C NMR (75.45 MHz, CD ₃ COC
D ₃ ): δ 24.26, 134.00, 134.77 MS m / z: 313 (M ⁺ ) HRMS: Calculated value of C ₉ H ₁₇ B ₁₀ Br 314.1445 Actual value 314.1483 Analysis result above Thus, the compound 2 obtained in this synthesis example is
1- (4-bromophenyl) -2 represented by the following chemical formula
-Methyl-1,2-carborane.

[0033]

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(Synthesis of Compound 4) The 1- (4-bromophenyl) -2-methyl-1,2- obtained in the above synthesis example.
Carborane (3.13 g, 10 mmol), catalytic amount of P
d (PPh ₃ ) ₄ (231 mg, 0.2 mmol), C
Dry T of a mixture of uI (38 mg, 0.4 mmol) and triethylamine (2.1 ml, 15 mmol)
An HF (50 ml) solution was prepared. To the obtained THF solution, trimethylsilylacetylene (2.1 ml, 15 m
mol) was added at 0 ° C under an Ar atmosphere to prepare a mixture, and the mixture was refluxed at 100 ° C for 24 hours. After evaporating the solvent, KF (2.32 g, 40 mmol) and KOH
(0.17 g, 3 mol) and methanol (100 m
l) The solution was added to the crude oil and stirred at room temperature for 2 hours.

Next, methanol was distilled off, and the residue was washed with brine / ether (20 ml / 20 ml) and extracted three times with ether (20 ml).

The ether extract was dried over MgSO ₄ and concentrated to give a yellow solid. Finally, the product was purified on a silica gel column using hexane as a developing solution to give 80% (2.0%).
A white solid (compound 4) was obtained with a yield of 6 g).

The ¹ H NMR spectrum, ¹³ C NMR spectrum and IR spectrum of the obtained compound 4 were
The characteristics are shown in the graphs of FIGS. 6, 7 and 8, respectively, and are summarized below.

IR (KBr): 3288, 2584, 2
^{563,1508,844,664cm -1 1 H NMR (300MHz,} CD 3 COCD 3): δ
1.79 (s, 3H), 3.76 (s, 1H), 7.
43 (d, 2H, J = 8.7 Hz), 7.57 (d, 2
H, J = 8.7 Hz) ¹³ C NMR (75.45 MHz, CD ₃ COC)
D ₃ ): δ 80.49, 82.97, 122.31,
123.39, 132.57, 134.46 MS m / z: 258 (M ⁺ ) HRMS: Calculated value for C ₁₁ H ₁₈ B ₁₀ 260.2339 Observed value 260.2324 From the above analysis results, in this synthesis example, The resulting compound 4 is
1- (4-ethynylphenyl)-represented by the following chemical formula
It was identified as 2-methyl-1,2-carborane.

[0039]

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

[0041]

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(Synthesis of Compound 5) 1- (4-Ethynylphenyl) -2-methyl-1,2 obtained in the above synthesis example.
-Carborane (51.6 mg, 0.2 mmol) in TH
The resulting solution was dissolved in F to prepare a solution (A), and 1 equivalent of nBuLi was added to this THF solution at 0 ° C. to obtain a purple solution.
The resulting solution was left at room temperature for 1 hour.

On the other hand, C ₆₀ (72 mg, 0.1 mmol)
Was dissolved in toluene to prepare a solution (B), and this solution was heated at 35 ° C. under an extremely dry nitrogen atmosphere.

The above solution (A) was gradually added to solution (B) to obtain a mixture. The mixture turned amber brown and was allowed to react overnight.

After the reaction, the mixture was added to CF ₃ COOH (2 m
After l) was added, the solvent was evaporated to give a crude brown-black solid. This solid was dissolved in CHCl ₃ and filtered through filter paper to give an amber brown solution and a fine solid (Compound 5). The solid is novel and not dissolved in solvents other than CS _2.

The CHCl ₃ was then evaporated and the brown solid was washed with hexane to remove excess compound 4 (43%).

The unreacted C ₆₀ (13%) was recovered from the obtained brown solid by flash chromatography (hexane developing solution, silica gel). The yield of compound 5 is 67
%Met.

The ¹ H NMR spectrum, ¹³ C NMR spectrum, IR spectrum and mass spectrum of the obtained compound 5 are shown in the graphs of FIGS. 9, 10, 11 and 12, respectively, and the characteristics are summarized below.

IR (KBr): 2,583,1685,1
508, 1458, 1429, 1209, 1182, 1
^{144,844,526cm -1 1 H NMR (300MHz,} CS 2 / OD 2 C
l ₂ ): δ 1.82 (s, 3H), 7.152 (s,
1H) (m, 4H) ¹³ C NMR (75 MHz, CD ₃ Cl / CS ₂ ): δ 151.292, 151.135, 147.41
0,147.146,146.479,146.23
1,146.207,146.050,146.03
3,145.638,145.546,145.49
0, 145.300, 145.259, 145.17
6,144.509,144.336,143.04
2,142.869, 144.440, 142.40
7, 141.904, 141.880, 141.84
7, 141.674, 141.509, 141.45
1,140.174,135.905,134.94
8, 107.487, 88.152, 61.919,5
5.318,22.788 mass electrospray Iona homogenization of in _{CH 2 Cl 2 (ESI),} CH 2 for compound 5 in Cl ₂ data: 977.4 (M- -H); 817.0
^{(M - - (1-Me} -1,2-C 2 B 10 H 11); 74
^{4.64 (M - - (1-} Me, 2-Ph-1,2-C 2
_{B 10 H 10); 257.3 (} 1- (CC-Ph), 2-M
_{e-1,2-C 2 B 10} H 10); 234.12 (1-M
e, 2-Ph, 1,2- C 2 B 10 H 10); 158.14
From (1-Me-1,2-C 2 B 10 H 10) above analysis results, the obtained compound 5 in Synthesis Example 1- hydro-2- [1- (4 represented by the following chemical formula -Ethynylphenyl)
-2-Methyl-1,2-carborane] fullerene.

[0050]

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[0051] The cyclic voltaic Bruno grams of the resulting compound 5 and C ₆₀ shown in the graph of FIG. 13. In the graph,
Curve a represents the cyclic voltammogram of compound 5, where compound 5 was 5 × in ortho-dichlorobenzene.
Used as 10 ⁻³ M. Curve b represents a cyclic voltaic Bruno grams of C _60, C ₆₀ ortho - was used as in-dichlorobenzene 2.5 × 10 ^-3 M.

The conditions are as follows.

[0053] 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 Curve a (compound 5) shows three quasi-reversible reduction waves similar to curve b (C ₆₀ ). Specifically, curve a shows three quasi-reversible reduction waves (E _red E _ox mV; −
1186: -549, -1657: -990, -233
4: -1550) and curve b (C ₆₀ ) shows three quasi-reversible reduction waves (E _red : E _ox mV; -1102).
-549, -1534: -1040, -2002: -1
599).

The presence of an irreversible oxidation wave at -165 mV corresponds to a conjugated spacer fragment. The observation of four distinct reduction waves for Compound 5 is consistent with the predicted electrochemical process of the two covalently linked scaffolds. The three reduction potentials of curve a for compound 5 are C
_It can be seen that there is a significant shift to a negative value from the reduction potential of curve b for ₆₀ . This is due to saturation of the double bond. This is described in the following literature. Helv. Chim. Acta. 1995, 78, 1334 (Bo
udon, C .; Gisselbrecht, J.-P; Gross, M .; Isaacs,
L .; Anderson, HL; Faust, R .; Diederich, F.), In H
andbook of Organic Conductive Molecules and Polyme
rs Nalwa HS, Ed (Chlistunoff, J .; Cliffel, D .;
Bard, AJ, John Wiley & Sons Ltd .; New York, 199
7; Vol. 1, Chapter 7), J. Am. Chem. Soc. 1994, 116, 1359.
(Suzuki, T .; Maruyama, Y .; Akasaka, T .; Ando, W.; Koba
yashi, K .; Nagase, S.).

In addition, the electrochemical behavior of compound 5 is C
It is dominated by a strong suction effect of ₆₀ clusters, charge withdrawal characteristics of carborane spacer backbone shows that ineffective in the presence of C _60.

[0056] The graph of FIG. 14 represents the UV absorption spectrum of the compound 5 and C ₆₀ of the present invention. In the graph, curve c represents the UV absorption spectrum of compound 5, and compound 5 was used at 10 ^-6 M in chloroform. Also,
Curve d represents the UV absorption spectrum of C _60, C ₆₀ was used as 5 × 10 ^-6 in chloroform.

As shown by the curve c, the absorption spectrum of the compound 5 / CH ₃ Cl in the UV-visible region shows a very weak absorption band at 430 nm due to the forbidden transition.
0 nm, with two large absorption bands at 257n
m and 330 nm. In chloroform,
Compound 4 is transparent in the UV-visible range and no absorption is observed.

FIG. 15 shows a fluorescence spectrum of the compound 5 of the present invention in chloroform. As shown in the graph, the fluorescence spectrum of compound 5 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 Raman scattering of chloroform. (Fluorescence is also present in THF and in CH ₃ CN).

In the double frequency range of 532 nm, no spectral absorption and / or emission is observed, and the β coefficient of compound 5 can be measured simultaneously to obtain the β value.

The graph of FIG. 16 shows the Ultra Rayleigh scattering (HRS) signal of Compound 5 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. β value is J.Phys.Re
Calculated with reference to the method described in v.1987, A36, 2210 (Kajzar, F .; Ledoux, I .; Zyss).

Note that four different number densities in the unit of 10 ¹⁴ cm ^-3 are shown, and the number densities of the curves e, f, g and h are 3.0, 6.0, 30 and 301, respectively. It is.

Based on the results shown in the graph of FIG. 16, the number density of the compound 5 and the quadratic coefficient I (2ω) / I
The relationship with ² (ω) is shown in the graph of FIG.

The β value for compound 5 of the present invention is 36
It is extremely large at 4 × 10 ⁻³⁰ esu. The β value of para-nitroaniline under the same conditions was 23 × 1.
0 ^-3 was found to be ^0.

[0064] The graph of FIG. 18 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.

[0065] The relation between the number density and the secondary coefficient of the C ₆₀ in chloroform at 293K in the graph of FIG. 19. Beta value of C ₆₀ is zero, which is due to the central symmetry structure of C _60.

Here, FIG. 20 summarizes χ / esu of the conventional inorganic and organic nonlinear optical materials. Note that FIG.
The organic compounds represented by abbreviations therein are represented by the following chemical formula.

[0067]

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Of these compounds, urea
Is a conventional standard substance, and its beta value is 0.1.
5 × 10 ⁻³⁰ esu.

Table 1 below summarizes beta values of typical examples of other conventional nonlinear optical materials.

[0070]

[Table 1]

Thus, it can be seen that the beta value of the hybrid compound of the present invention is extremely high even when compared with the beta values of typical examples of conventional inorganic and organic materials.

The nonlinear optical properties of the hybrid rod compound 5 of the present invention are very interesting. By forming a suitable donor and the charge transfer complex, collapsed the center of symmetry of the C _60, have been speculated to induce significant secondary optical non-linear properties (e.g., J.Phys.Chem.1992,96 , 53
0 (Wang, Y .; Cheng, L.-T.)). On the other hand, the rod hybrid compound 5 of the present invention shows a large β value without forming a charge complex.

The direct utility of the hybrid rod compound 5 of the present invention is that the corresponding fullerene carborane rigid rod compound can be easily synthesized using the corresponding meta- and para-carborane clusters instead of ortho-carborane. And obtain similar types of compounds that can be used for further studies. Further, various conjugated bridging aromatic groups (thiophene, aniline) provide C
It is also possible to link ₆₀ with carborane, especially its metallocarborane anion complex, to form a triad.

It is conceivable that the present invention is also applied to a third-order optical nonlinear material of a fullerene-carborane (or metallocarborane) hybrid rod.

[0075]

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 great industrial value.

[Brief description of the drawings]

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

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

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

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

FIG. 5 is an IR spectrum of Compound 2.

FIG. 6 is a ¹ H NMR spectrum of Compound 4.

FIG. 7 is a ¹³ C NMR spectrum of Compound 4.

FIG. 8 is an IR spectrum of Compound 4.

9 is a ¹ H NMR spectrum of Compound 5. FIG.

FIG. 10 is a ¹³ C NMR spectrum of Compound 5.

FIG. 11 is an IR spectrum of Compound 5.

FIG. 12 is a mass spectrum diagram of compound 5.

Cyclic Volta Bruno grams of 13 compounds 5 and C _60.

[14] UV absorption spectrum of the compound 5 and C _60.

FIG. 15 is a fluorescence spectrum diagram of compound 5 in chloroform.

FIG. 16 is a graph showing a super-Rayleigh scattering signal of compound 5 in chloroform.

FIG. 17: Number density and quadratic coefficient I (2ω) / I of compound 5
² is a graph showing a relationship with (ω).

Figure 18 is a graph diagram showing the HRS signal of C _60.

Figure 19 is a graph showing the relationship between the number density and the secondary coefficient of C _60.

FIG. 20 shows Δ / of conventional inorganic and organic nonlinear optical materials.
The figure showing esu.

Claims (2)

(57) [Claims] A fullerene-carborane rigid rod hybrid compound represented by the following chemical formula : Embedded image 2. 1- (4-bromophenyl) -1,2-ca
The reaction of ruborane with methyl iodine gives 1- (4-bromo
To obtain (mophenyl) -2-methyl-1,2-carborane
Step 1- (4-bromophenyl) -2-methyl-1,2
-Reaction of carborane with trimethylsilylacetylene
1- (4- (trimethylsilylethynyl) phenyl)
B) obtaining 2-methyl-1,2-carborane, wherein said 1- (4- (trimethylsilylethynyl) phenyl
De) -2-methyl-1,2-carborane,
1- (4-ethynylphenyl) -2-methyl-1,2-
Obtaining a carborane, and the 1- (4-ethynylphenyl) -2-methyl-1,
2-Carborane lithium acetylide was obtained,
To react with 1-hydro-2- [1- (4-E
Tinylphenyl) -2-methyl-1,2-carborane]
Fullerene-carbora comprising a step of obtaining fullerene
A method for synthesizing a rigid rod hybrid compound.