JPH0441475A - Aminonitrosulfide compound and non-linear optical material - Google Patents

Abstract

NEW MATERIAL:A compound shown by formula I (A is electron attractive group; n is 1-4). USE:A non-linear optical material useful for electro-optical device, second harmonic generation device, light integration device, light memory light source, laser printer light source and optical switch. PREPARATION:2,4-Dichloronitrobenzene and p-aminothiophenol are dissolved in DMSO and reacted with sodium carbonate in a nitrogen flow at about 100 deg.C to give a compound shown by the formula.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to electro-optical devices, second harmonic generation (SHG)
The present invention relates to novel compounds and nonlinear optical materials useful for devices, optical integrated devices, optical memory light sources, laser printer light sources, optical switches, etc.

[Prior Art] In recent years, materials that have a nonlinear optical effect - a phenomenon in which when intense laser light is incident on a material, an emitted light with a different component from the incident light is obtained due to the interaction - have attracted attention. There is. Such materials are generally known as nonlinear optical materials and are described in detail in, for example:

“Non1iner 0pt1eal Property
ies of Organic and Polyver
ic Materials″A CS SYMPO8
IUM SERIES 283. Davld JJ111
iams edition (American Chemical 5o
c1ety, 1983), “Organic Nonlinear Optical Materials”
Supervised by Masao Kato, Nakanishi Department (C.C.C. Co., Ltd., 198
3 years), "Organic Electronic Materials" edited by Akio Taniguchi (Science Forum Publishing, 1986).

One of the applications of nonlinear optical materials is second harmonic generation (SHG) based on second-order nonlinear optical effects, and wavelength conversion devices using sum frequency and difference frequency. Potassium dihydrogen phosphate (KD
P), ammonium dihydrogen phosphate (ADP), lithium niobate, and the like. However, in recent years, it has become known that π-electron conjugated organic compounds having an electron-donating group and an electron-withdrawing group have various performances as nonlinear optical materials that far exceed those of the above-mentioned inorganic materials.

In general, in the case of organic compounds, each molecule exhibits a nonlinear optical response, and the nonlinear optical performance of the molecule is determined by its molecular hyperpolarizability: β (molecular hyperpolarizability).
Although it depends on the size of P-nitroaniline, even if it shows high second-order nonlinear performance in the molecular state (i.e., has a large β), it becomes crystalline. Due to the central symmetry of the molecular arrangement, many molecules do not exhibit any second-order nonlinear optical effects in the crystalline state. Furthermore, by introducing a methyl group into the ortho position of this P-nitroaniline, MNA (2-methyl -4 nitroaniline) has a large SHG tensor du [B,F
, Levine, et at, J.

AI)I)1. Phys, 50.2528 (1970)
], this component does not satisfy the phase matching condition for efficiently extracting SHG, so it is difficult to effectively utilize this large nonlinear optical performance.

Furthermore, it is difficult to obtain a single crystal of MNA, and there are many problems in applying it as a device.

In addition, asymmetric carbon atoms are introduced into known SHG active skeletons [
J, L, Oudar, et al, J, Appl Ph.
ys, 48°2699 (1977)], and high-performance molecules are dispersed in a polymer and poled by an electric field (
Methods such as those disclosed in Japanese Patent Application Laid-Open No. 186942/1983 have been considered, but good results have not always been obtained.

[Problems to be Solved by the Invention] In view of the above circumstances, an object of the present invention is to provide a novel compound and a nonlinear optical material that exhibit high nonlinear optical effects.

[Means for Solving the Problems] The present inventors have conducted extensive research to solve the above problems, and found that a specific aminonitrodiphenyl sulfide derivative is effective, leading to the present invention. .

That is, the present invention (1) The following general formula (I) (^).

(In the formula, A is an electron-withdrawing group that may be the same or different, n
represents an integer from 1 to 4).

(2) The following general formula (I) (A)n (wherein A is an electron-withdrawing group which may be the same or different, n
represents an integer from 1 to 4) This is a nonlinear optical material characterized by being made of an aminonitrosulfide compound represented by

Examples of the electron-withdrawing group include an alkyl group, a halogen atom, a nitro group, a cyano group, etc., and may contain a plurality of different types of these substituents.

Next, preferred examples of compounds in the present invention are shown below. However, the present invention is not limited to these.

[Example of Compound O2 NO2F NO2 O2 The compound of the present invention can be synthesized, for example, by the following method.

[Synthesis Example 1] Synthesis of Compound Example 4.5 2. 1.03 g of 4-dichloronitrobenzene and 0.80 g of p-aminothiophenol were dissolved in 030 ml of DNS, 79 g of Na 2 CO was added, and the mixture was heated at 100° C. under a nitrogen stream. It was heated for 2 hours.

After the reaction, the mixture was poured into water and extracted with chloroform. After drying with magnesium sulfate and removing chloroform under reduced pressure,
A mixture of Compound Example 4.5 was obtained.

The reaction mixture was recrystallized from toluene to obtain a mixture of Compound Example 5 as black crystals and a mixture of Compound Example 4 as yellow crystals.

After separating the crystals, Compound Example 5 was purified by sublimation, and Compound Example 4 was extracted and separated using chloroform. The yield of Compound Example 5 was 15%, and the yield of Compound 4 was 70%.

Compound Example 4 was obtained as yellow crystals with a melting point of 104°C,
Compound Example 5 was obtained as yellow crystals with a melting point of 128°C. The physical property values of each are shown below.

Compound Example 4 Compound Example 5 IR (kBr) 3472.3380 (-NO2'')
3488.3382 (-NO2) (eg+-blind)
1497.1340 (-NO2) 1584
．． 1332 (-NO2) original HI (%) Actual value Calculated value
Actual value Calculated value C52,2154,5454,0154
,54H3,083,433,123,43 N 9.90 10.60 10.45 10.6
0 [Synthesis Example 2] Synthesis of Compound Example 6 3. Dissolve 1.29 g of 4-dichloronitrobenzene and 1.08 g of p-aminothiophenol in DMSO, and dissolve N
85 g of a 2 CO was added and heated at 100° C. for 3.5 hours under a nitrogen stream. After repulsion, the mixture was poured into water, extracted with chloroform, and dried over magnesium sulfate. Chloroform was distilled off under reduced pressure to obtain yellow crystals. Since this crystal was a mixture with the raw material, it was separated using a syringe column (solvent: toluene), and compound example 6 was obtained as yellow crystals.
．． 80g was obtained (yield: 8B%). The melting point of the crystals obtained by recrystallization with ethanol was 133 to 134°C.

IR (kBr) 3464.3378 (-NO2)
(cm-') 1495.1340 (-NO2)
Elemental analysis (%) Actual value Calculated value C54,8354,54 H3,233,43 N 10.90 10.60 [Example: The nonlinear optical performance of the above compound was measured.

Second-order harmonic generation (
SHG) measurements to S, Kurtz and T, T.

Perry J, Appl, phys, 39.3798
(198g). In this method, the compound powder to be measured is irradiated with a strong laser beam, and the intensity of the generated SHG is measured against a reference material, and the approximate second-order nonlinear performance can be estimated.

We used a high-power Nd":YAG laser (250 mJ/pulse, pulse width ~20 ns) as the light source laser. (The oscillation wavelength of the Nd":YAG laser is 1.0
84μ■, and when this light is irradiated onto an SHG-active material, a green SHG of 532n- is obtained.) The detector at this time is a photomultiplier tube, which cuts the laser light with an infrared absorption filter and detects interference. S of 532ns by filter
Only HG was taken out.

At this time, the particle size of the sample was not screened, and the reference material was urea with an average particle size of about 100 μm.

(*NH4H2PO4ammonium dihydrogen phosphate) As is clear from the examples, the compound of the present invention is effective as a nonlinear optical material, and for example, by making this material into a single crystal, it can be applied to an SHG device as shown in Figure 1. can.

[Effects] As explained above, the present invention makes it possible to provide a novel high-performance nonlinear optical material.

[Brief explanation of drawings]

FIG. 1 is a diagram schematically showing an example of an SHG device using the nonlinear optical material of the present invention. ■...Semiconductor laser, 2...Single crystal of the material of the present invention.

Claims (2)

[Claims] (1) The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, A is an electron-withdrawing group that may be the same or different, n
represents an integer from 1 to 4). (2) The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, A is an electron-withdrawing group that may be the same or different, n
represents an integer from 1 to 4). A nonlinear optical material comprising an aminonitrosulfide compound represented by: