JP3530918B2 - Polydipyridyl diacetylene derivative and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polydipyridyl diacetylene derivative which is a third-order nonlinear optical material useful for application to optical switches, optical memories, phase correction elements, etc.
The manufacturing method is related.

[0002]

2. Description of the Related Art Since the advanced information society requires a large amount of information transmission, processing, and computation, the next generation will leap forward from the era of electronics in this century, and the high speed of light, parallelism, high density, and electromagnetic wave. It is expected that we will enter the age of photonics, which makes use of characteristics such as resistance that are different from electrons. In order to support this photonics, it is necessary to develop a high-performance optical material and its elementization technology as a technology for controlling light, and a nonlinear optical material is drawing attention as the material.

Particularly, since the third-order nonlinear optical material has properties such as nonlinear refractive index effect, phase conjugate wave generation, and optical stability, it is expected to be applied to optical switches, optical memories, phase correction elements and the like. .

The photoresponsiveness of such a third-order nonlinear optical material can be understood as electric polarization of a substance induced by an oscillating electric field of incident light, and when light having a strong electric field intensity such as laser light is used. Second-order, third-order, etc. non-linear polarization is observed. The third-order nonlinear susceptibility χ ⁽³⁾ is
It has a close relationship with refractive index modulation, whether it is inorganic or organic,
The development of materials with large χ ⁽³⁾ values has become an important research topic for the photonics era.

Known conventional third-order nonlinear optical materials of this kind are, for example, GaAs and fine particle-doped glass as an inorganic material, and polyphenyleneethynylene and polydiacetylene which are π-conjugated polymers as an organic material. There is.

[0006]

[Problems to be Solved by the Invention] However, GaA
In s, although the χ ⁽³⁾ value is large, there is a problem that the responsiveness is poor. In addition, for fine-particle-doped glass, χ ⁽³⁾
Although the value and responsiveness are both medium and well balanced, there is a problem that it is difficult to process.

On the other hand, polyphenylene ethynylene and polydiacetylene are faster in response than inorganic materials and various molecular designs are possible, and since they are polymers, they can be used as devices such as thin films and waveguides. Although it has an advantage that it can be easily processed, there is a problem that the χ ⁽³⁾ value is low.

The present invention has been made in view of the above problems, and an object thereof is to provide a polydipyridyl diacetylene derivative having a large third-order nonlinear susceptibility χ ⁽³⁾ and a method for producing the same. And

[0009]

In order to achieve the above object, the means of using the polydipyridyl diacetylene derivative of claim 1 is that the general formula is represented by the above chemical formula 1 .

[0011]

[0012]

[0013] It is an unit of the manufacturing method of the poly dipyridyl diacetylene derivative according to claim 2, general formula wherein reduction
It is to polymerize the dipyridyl diacetylene derivative represented by 2 by irradiating with ultraviolet rays or radiation.

A method of producing the polydipyridyldiacetylene derivative according to claim 3 is that the alkyl group is a methyl group.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below. The dipyridyldiacetylene derivative as the monomer according to this embodiment has a general formula of the formula 1 [wherein R is an alkyl group, X ⁻ is CF ₃ SO ₂ O ^— (Tf
O ⁻ : triflate anion), n represents an integer of 2 or more], and is a quaternary chlorinated 1,4-bis (4-alkylpyridinium) butadiyne triflate.

The alkyl group is a monovalent hydrocarbon group represented by C _n H _{2n + 1-} , and has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms (lower alkyl group). )
The straight chain structure or branched structure of

This dipyridyl diacetylene derivative produces a plate-like single crystal in a packed state suitable for solid phase polymerization. The third-order nonlinear susceptibility χ ⁽³⁾ is 10 ^-12 esu
There is an advantage that it takes a relatively large value. In addition,
If the number of carbon atoms in the alkyl group exceeds 20, it is not preferable because it becomes too bulky and it becomes difficult to obtain a packed state.

In order to produce this dipyridyldiacetylene derivative, the dipyridyldiacetylene represented by the chemical formula 3 is represented by the general formula CF ₃ SO ₂ OR (wherein R represents an alkyl group). Alkyl triflate (alkyl trifluoromethanesulfonate) may be reacted.

That is, about 2 equivalents of alkyl triflate is dropped into a dichloromethane solution of dipyridyl diacetylene or the like, and the mixture is stirred for several tens of minutes. After the formed salt is separated by filtration and then purified by, for example, recrystallization, a plate-like single crystal of the above-mentioned dipyridyldiacetylene derivative can be obtained.

As described above, since it is only necessary to react dipyridyldiacetylene with an alkyl triflate, there is an advantage that a dipyridyldiacetylene derivative can be easily produced. Here, when the alkyl group is a methyl group, inexpensive methyl triflate (methyl trifluoromethanesulfonate) can be used, so that there is an advantage that the production cost of the dipyridyl diacetylene derivative can be reduced.

If the dipyridyldiacetylene derivative is irradiated with ultraviolet rays or radiation for several hours to several tens of hours and polymerized, poly (1,4-bis (4-alkylpyridinium) butane as a polydipyridyldiacetylene derivative is polymerized. A single crystal of diintriflate can be obtained. Examples of the radiation include γ rays, X rays, β rays, electron rays and the like.

As described above, since the polymer single crystal can be obtained by simply irradiating the dipyridyldiacetylene derivative as a monomer with ultraviolet rays or radiation, it is easy to manufacture and can be used as a device such as a thin film or a waveguide. Also has the advantage of being suitable. Also in this case, when the alkyl group is a methyl group, it is possible to use a monomer that can be produced at low cost, which is advantageous in that the production cost can be reduced.

[0023]

EXAMPLES The present invention will now be described in more detail with reference to examples, but the present invention is not limited to the examples.

As shown in FIG. 1, 1,4-bis (4-methylpyridium) butadiyne triflate whose alkyl group is a methyl group was used as a monomer M.

[Production of Monomer] This monomer M was prepared by converting dipyridyldiacetylene prepared by a known method using 4-bromopyridine hydrochloride shown in FIG. 1 as a starting material into methyl triflate (methyltrifluoromethanesulfonate) to give It was prepared by chlorination. That is, 2.0 g of dipyridyl diacetylene was dissolved in 50 mL of dichloromethane, 3.3 g of methyl triflate was added dropwise to this solution at 0 ° C. (in an ice bath), and the mixture was stirred for 30 minutes. Then, the formed salt was filtered off, and about 2 g thereof was added to 10 mL of dichloromethane.
And 30 mL of acetonitrile in a mixed solvent [acetonitrile: dichloromethane = 3: 1 (volume ratio)],
It was left to stand in a constant temperature bath at 5 ° C for 2 to 3 days. By this recrystallization purification, a 1.3 mm × 1.4 mm plate-shaped single crystal was obtained.

From the result of the X-ray structure analysis shown in FIG. 2, the three-dimensional crystal structure of the obtained monomer M was in a packing state suitable for solid phase polymerization. The physicochemical properties of this monomer M are shown below.

Yield: 100% Melting point: 240 ° C. UV-visible absorption spectrum (see FIG. 3): Maximum absorption wavelength λ _max = 323 (nm) Molar extinction coefficient ε = 331 (l · mol ⁻¹ · cm ⁻¹ ) ( λ
= 532 nm) Nuclear magnetic resonance spectrum (DMSO-d ₆ , δ value, pp
m): 4.35 (CH ₃ , 6H), 8.43 (py-H, 4H),
9.11 (py-H, 4H)

Further, the concentration dependence of | χ ⁽³⁾ | ² in the solution state of the monomer M using acetonitrile as a solvent is determined by the phase-conjugated degenerate four-wave mixing (DFWM) method [wavelength: 532].
nm, pulse width: 40 ps, reference substance: CS ₂ (2.9
× 10 ⁻¹² esu)]. The result is shown in FIG.

[Calculation of Second Molecule Hyperpolarizability γ] The second molecule hyperpolarizability γ was calculated by fitting the relationship plot of | χ ⁽³⁾ | ² of the solution and the concentration with the following formula. │χ ⁽³⁾ _m │ = χ ⁽³⁾ _s + f ⁴ N ｜ γ ｜ _{・ ・ ・} where χ ⁽³⁾ _s : solvent (acetonitrile) third-order nonlinear susceptibility f = (n ² +2) / 3: Lorentz Local field correction coefficient N: Molecular number density of monomer M

This equation can be transformed into the following equation. | Χ ⁽³⁾ _m | = _{^{[(χ (3) s · r}} + f 4 Nγ r) 2 + (f 4 Nγ i) 2 ] ^1/2 ...... _{^{However, χ (3) s · r}} : χ (3 ⁾ the real part of _s γ _r: real part of γ γ _i: the imaginary part of γ

Since the relationship plot is a curve, the equation can be derived as: [(Χ ⁽³⁾ _m ) ² − (χ ⁽³⁾ _{s · r} ) ² ] = [f ⁸ (γ ² _r + γ ² _i )] N ² + (2χ ⁽³⁾ _{s · r} f ⁴ γ _r ) N ……

The equation is a least squares method (quadratic equation, y = ax ² +
bx), coefficients a and b were obtained by fitting a = f ⁸ (γ ² _r + γ ² _i ), b = 2χ ⁽³⁾ _{s · r} f ⁴ γ _{r to} the equation y = ax ² + bx. The results are shown in Table 1 below.

[0033]

[Table 1]

As is clear from Table 1, γ of the monomer M
The value is 7.1 × 10 ⁻³⁴ esu, the real part has a negative sign, and the imaginary part has a positive sign, indicating that the response mechanism exhibits two-photon absorption. The χ ⁽³⁾ value calculated from the γ value of the solution was 3.1 × 10 ^-12 esu.

[Production of Polymer by Solid Phase Polymerization] As shown in FIG. 1, a single crystal of the monomer M was irradiated with ultraviolet rays at room temperature in the air for 10 hours using an ultraviolet irradiation device (EHB-WI300, manufactured by Eikosha). did. Then, GPC (gel permeation chromatography) measurement was performed. The results are shown in Table 2 below.

[0036]

[Table 2]

As is clear from Table 2, the number average molecular weight of the obtained polymer P was 14,000, and the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight) was 1.21.

[0038]

As described above , according to the invention of claim 1 ,
Since the polydipyridyldiacetylene derivative represented by the general formula 1 is a polymer single crystal, it is suitable for use as an element such as a thin film or a waveguide, and its χ ⁽³⁾ is 10
-It has the advantage of taking a relatively large value of ¹² esu or more.

[0040]

[0041]

According to the invention of claim 2 , the general formula becomes
Since the polymer single crystal can be obtained by simply irradiating the dipyridyldiacetylene derivative represented by 2 with ultraviolet rays or radiation, it is easy to manufacture, and is also suitable for forming devices such as thin films and waveguides. There are advantages.

According to the third aspect of the present invention, since the alkyl group is a methyl group, it is possible to use a monomer that can be produced at a low cost, which is advantageous in that the production cost can be reduced.

[Brief description of drawings]

FIG. 1 is an explanatory view showing a manufacturing process up to a polymer in Examples.

FIG. 2 is a three-dimensional crystal structure model diagram obtained by X-ray structural analysis of a monomer.

FIG. 3 is an ultraviolet-visible absorption spectrum chart of a monomer.

FIG. 4 is a graph showing the concentration dependence of | χ ⁽³⁾ | ^{2 in} a monomer solution state.

[Explanation of symbols]

M monomer (dipyridyl diacetylene derivative) P polymer (polydipyridyl diacetylene derivative)

─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-9-227552 (JP, A) JP-A-6-271624 (JP, A) US Patent 5037916 (US, A) Rikagaku Dictionary, Japan, Iwanami Co., Ltd. Bookstore, February 20, 1998, 5th edition, page 974 (58) Fields investigated (Int.Cl. ⁷ , DB name) C07D 213/00-213/06 REGISTRY (STN) CA (STN)

Claims (3)

(57) [Claims] 1. A general formula: (In the formula, R is an alkyl group, X ⁻ is CF ₃ SO ₂ O ⁻ , and n is
Polydipyridyl diacetate represented by 2 or more )
Tylene derivative . 2. A general formula: (Wherein, R is an alkyl group, X ^- is CF ₃ SO ₂ O ^- represents a)
The dipyridyl diacetylene derivative represented by
Is characterized by being polymerized by irradiation with radiation.
A polydipyridyl diacetylene derivative according to claim 1.
Manufacturing method . 3. The polydipyridyl diacetylene according to claim 2, wherein the alkyl group is a methyl group.
Method for producing derivative .