JPH03293334A - Nonlinear optical material - Google Patents

Abstract

PURPOSE:To obtain an org. material having high nonlinear optical sensitivity and superior transparency by incorporating a 1, 3-diketone deriv. represented by a prescribed formula. CONSTITUTION:This nonlinear optical material contains a 1, 3-diketone deriv. represented by formula I, wherein Y is Br or H, each of R<1> and R<2> is an org. substituent selected among amino, 1-12C substd. amino, cyclic amino, alkyl, halogen-substd. alkyl, alkoxy, halogen-substd. alkoxy and mercaptoalkoxy, n is 1-5 as the number of R<1>. in the case of n >=2, plural R<1>'s may be different from each other, m is 0-5 as the number of R<2>, in the case of m >=2, plural R<2>'s may be different from each other and each of A and B is a cyclic org. group which is a residue of arom. hydrocarbon or hetero arom. hydrocarbon.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a nonlinear optical material used for optical information, optical communication, etc. Regarding. For example, it can be used in wavelength conversion elements for semiconductor lasers, measuring instruments, information transmission through optical fibers, and the like.

(Prior Art) Laser light has r1 chromaticity and directivity, that is, coherent property, and therefore exerts a specific interaction with substances. This interaction is known as a nonlinear optical effect, and causes phenomena such as harmonic generation, the Kerr effect, optical mixing, and parametric amplification. In particular, second-order and third-order nonlinear optical effects can be expected to have relatively large nonlinear susceptibilities, so they can be applied to information processing, optical communications, etc.

Conventionally, KDP (KH2PO
4), ADP (NHJ+PO4), L iN b
Inorganic materials such as 03 have been used and applied to some measuring instruments. However, it is difficult to apply it to light-related applications due to reasons such as high purity single crystals, high price, poor light damage resistance, deliquescent property, and low nonlinear optical susceptibility. there were.

In recent years, it has been discovered that organic materials have superior nonlinear optical effects compared to inorganic materials, and since then, organic materials, which have a high degree of freedom in molecular design, have been attracting attention. In particular, C -T (Charge-Tr
It has been thought that a large nonlinear susceptibility can be expected because the ansfer type percussion compound induces a large molecular hyperpolarizability.

However, the crystal structure of an organic compound is determined by intermolecular interactions, ie, intermolecular forces such as hydrogen bonds and van der Waals interactions. In the case of C-T type molecules having strong electron-withdrawing substituents and electron-donating substituents as described above, strong dipole-dipole interactions between molecules work to stabilize the crystal, that is, bimolecular dipoles. It is easy to form a crystal structure in which the children cancel each other out. Such a crystal structure is a centrosymmetric crystal as a molecular assembly, and is therefore nonlinearly optically inactive.

Therefore, the following method is used as a means of disrupting the central symmetry of such a crystal structure. In other words, substituents with large hydrogen bonding properties that can control molecular orientation such as hydroxyl groups, carboxyl groups, and amino groups, bulky substituents that significantly change the molecular structure due to steric hindrance, and optical substituents such as amino acids or amino acid derivatives. In addition to active substituents (D or pentad), methods of inducing non-centrosymmetric properties have been implemented by conjugation, such as complexes with clathrates.

Further, the following points are listed as necessary conditions for the application of the second-order nonlinear optical material as a nonlinear optical element.

■ Extremely high nonlinear optical susceptibility ■ High photoresponse speed ■ Excellent laser light transparency ■ Light damage resistance ■ Phase matching ■ Crystallinity (aJ ability for single crystal synthesis, etc.) ■ Mechanical strength ■ ■ Chemically stable [phase] with moisture resistance and other properties! ! #Nigital properties (problem to be solved by the invention) NPs with high hyperpolarizability and no central symmetry achieved by introducing hydrogen-bonding substituents and optically active substituents
In the case of C--T type compounds such as P and molecules with long π-electron conjugation, large second-order nonlinear susceptibility can be expected, but they suffer from drawbacks such as lack of transparency. Therefore, there was a drawback that the usable wavelength range was limited.

(Means for Solving the Problems) The present invention was carried out to solve the problem described in -1-, and provides an organic compound that achieves a large nonlinear optical susceptibility and has excellent transparency. It is.

In order to achieve the object set forth in item L, the present invention has the following configuration. That is, the present invention provides 1 represented by the following general formula [1],
This is a nonlinear optical material characterized by containing a 3-diketone derivative.

(In the formula, Y is B or hydrogen, and the substituents R' may be different or the same (amino, group, substituted amino group substituted with a group having 1 to 12 carbon atoms, ring rod amino group, An organic substituent selected from an alkyl group, a halogen-substituted alkyl group, an alkoxy group, a halogen-substituted alkoxy group, and a mercaptoalkoxy group, where n indicates the number and is 1 to 5, and R2 is the same organic substituent as R1. m represents the number and is O to 5. A and B are ring organic groups and represent residues of aromatic hydrocarbons or heteroaromatic hydrocarbons.

) In the 1,3-diketone derivative of the present invention, the bromine group at the 2-position is characterized as a functional organic substituent (orientation control group) that can induce non-centrosymmetricity, which is a sufficient condition for SHG activity, in the crystal state. Moreover, since it has an electron-donating group and an electron-withdrawing group in the molecule, optical nonlinearity can be increased. Introducing an electron-donating group at the ortho or para position of the aromatic ring is particularly effective because it increases the resonance effect due to charge transfer interaction.

In the present invention, in addition to the organic substituents R1 and R2, other substituents may be appropriately introduced as necessary to finely adjust the performance of the compound of the present invention.

Other substituents referred to in the present invention include amino, monomethylamino, monoethylamino, dimethylamino, diethylamino, n-butylamino, t-
Amine groups such as butylamino groups, ring amino groups such as piperidino, pyrrolidino, and morpholino, normal alkyl groups having 1 to 12 carbon atoms, alkyl groups such as t-butyl groups, alkyl groups containing optically active carbon, carbon atoms 1 to 12 normal alkoxy groups, t-butoxy groups, alkoxy groups containing optically active carbon atoms, mercapto normal alkoxy groups having 1 to 12 carbon atoms, t-thiobutoxy groups, and mercapto alkoxy groups containing optically active carbon atoms. In addition to groups, hydroxy groups, mercapto groups and halogens can be used. Examples of the electron-withdrawing group include a nitro group, a cyano group, a trifluoromethyl group, an incyanate group, a sulfonyl group, a carboxyl group, a carboxylic acid ester group, an acetylamino group, and a halogen.

The aromatic hydrocarbon residues and heteroaromatic hydrocarbon residues referred to in the present invention are benzene ring, naphthalene ring, anthracene ring, biphenyl ring, terphenyl ring, thiazole ring, furan ring, thiophene ring, virol ring, and pyridine ring. , pyrimidine ring, pyrazine ring, pyridazine ring, triazine ring,
Examples include a tetrazine ring.

The organic nonlinear optical material of the present invention can be synthesized using the formula [2], for example.

That is, in formula [2], 1,3-diphenyl-1,3-
It can be synthesized by (a) bromination using a propanedione-like conductor as a starting material.

(Example) Hereinafter, the present invention will be explained in more detail according to Examples.
The present invention is not limited to these examples.

Second harmonic generation (SHG) is measured using the powder method (S).
Kurz, T., T., Perry, 39.3798 (1
9H)). The light source used for measurement was Nd:
This is a YAG laser, which irradiates a powder sample with a laser beam with a fundamental wavelength of 11064n and generates a double wave (532n).
m) was detected using a spectrometer. A schematic diagram of the second harmonic generator is shown in FIG.

The powder samples used were those purified by iU crystals using methanol, ethanol, hexane, acetone, ethyl acetate, and toluene and used as they were.

17500 vaQ - Dry chloroform in Ronas flask 3
Add 00 mQ, 1-(4-chlorophenyl)-3-
(4-methoxyphenyl)-L3-propanedio 710
g (34.67mM) and completely dissolved. After cooling under a nitrogen stream (0°C), 11.85 g of bleaching solution (7
2.7mM) was added dropwise little by little. After reacting at 0°C for 1 hour and at room temperature for 1 hour, the solvent was removed using an evaporator and the crystals were collected. The obtained crude crystals were washed with methanol and purified into Ff crystals using methanol to obtain plate-shaped white crystals 15.
．． 21 g (yield 98%) was obtained.

The compound was confirmed using nuclear magnetic resonance spectrum, infrared absorption spectrum, and elemental analysis.

When the obtained bromine body (Ml) was measured at 880 intensity by the above method, it was 15.8 (acetone, hereinafter abbreviated as a), 15.2 (ethanol, hereinafter abbreviated as a), SH of 13.0 (toluene, hereinafter abbreviated as C), 24.7 (ethyl acetate, hereinafter abbreviated as d)
We were able to confirm the occurrence of G. The numbers in parentheses indicate the solvent used for recrystallization.

1 500 w ('- Dry chloroform 3 in Ronas flask)
00- and 1-(4-ethoxyphenyl)-3-(
4-methoxyphenyl)-1,3-propanedio 712
．． 8g (42.28mM) was added and completely dissolved. After cooling under a nitrogen stream (0°C), 14.21 g of bromine solution
(88.8mM) was added dropwise little by little. 1 hour at 0℃
After reacting at room temperature for 1.5 hours, the solvent was removed using an evaporator and the crystals were collected. The obtained crude crystals were washed with methanol and then purified by recrystallization with methanol to obtain 17.34 g of plate-shaped white crystals (yield: 90%).

The compound was confirmed using nuclear magnetic resonance spectrum, infrared absorption spectrum, and elemental analysis.

The compound was confirmed by nuclear magnetic resonance spectrum, infrared absorption spectrum, and elemental analysis.

The obtained dibrome compound (N[L2) was converted to 8 by the above method.
When 80 intensity was measured, it was 2.5(a) for urea.
), 1.7(b), 3.5(c), 8.8(d) SH
We were able to confirm the occurrence of G.

Support 91 500- Dry chloroform in a two-necked eggplant flask 300-
and 1-(3-chloro-4-methoxyphenyl)-
3-(3-bromo-4-methoxyphenyl)-1,3-
Propanedione 15. Og (37,7405mM) was added to form a suspension.

After cooling under nitrogen stream (-5℃) Bromine solution 13.28g
(83,0291 mM) was added dropwise little by little. After reacting for one hour at -5°C and returning to room temperature, the solvent was removed using an evaporator to obtain pale yellow crystals. The obtained crystals were washed with methanol and then purified by recrystallization with methanol to obtain 20.81 g (99%) of white fit crystals.

The compound was confirmed using nuclear magnetic resonance spectrum, infrared absorption spectrum, and elemental analysis.

The 880 intensity of the obtained novel compound [3] was measured using the method described in U.S.A., and the intensity was 21.9 (a) for urea.
SH of 3.7(b), 19.6(c), 28.9(d)
We were able to confirm the occurrence of G.

LLL1 200IIIQ Dry chloroform in a Nilon flask 3
00 Misaki was added thereto, and 12.5 g (35,4207 mM) of 1-(4-mercaptomethoxyphenyl)-3-(2,4-dichlorophenyl)-1,3-propanedione was added to form a suspension.

After cooling under nitrogen stream (-5°C) bromine solution 12.47g
(77,9255mM) was added dropwise little by little. -5℃
After returning to room temperature for one hour and reacting for a while, the solvent was removed using an evaporator to obtain pale yellow crystals. The obtained crystals were washed with methanol and then purified by recrystallization with methanol to obtain 18.00 g (99%) of white needle crystals.

The compound was confirmed using nuclear magnetic resonance spectrum, infrared absorption spectrum, and elemental analysis.

The obtained dibrome compound (Nα4) was converted to 88 by the bipedal method.
f of 0 intensity! When Ill determination was carried out, it was 24 for urea.
．． 7(a), 5.8(b), 11.7(c), 23. E
3(d) SHG generation could be confirmed.

Fruit' 1 sex 5 knee LL Synthesis of F was carried out in the same manner as in Examples 1 to 4, and Examples 1 to 4
SHG was measured in the same manner.

The SHG measurement results are shown in Tables 1-6.

1,-(4-chlorophenyl)-2-dibromo3-
(3-chloro-4-methoxyphenyl)-1,3-propanedione (Nf15. Example 5), ■-(2-hydroxy-5-chlorophenyl)-2-dibromo-3-(4
-mercaptomethoxyphenyl)-1,3-propanedione cme, Example 6), 1-(3,4-dichlorophenyl)-2-dibromo-3-(3-bromo-4-methoxyphenyl)-1,3- Propanedione (N117. Example 7), 1-(3-chloro-4-methoxyphenyl)
-2-dibromo-3-(4-mercaptophenyl)-1
, 3-propanedione (N[L8. Example 8), 1-(
3-bromo-4-methoxyphenyl)-2-dibromo-
3-(4-mercaptomethoxyphenyl)-1,3-propanedione [9, Example 9), 1-(3-chloro-4
-methoxyphenyl)-2-dibromo-3-(4-(N
, N-dimethylaminophenyl))-1,3-propanedione (Nα10. Example 10), 1-(3-fluoro-4-methoxyphenyl)-2-dibromo-3-(4-
Mercaptomethoxyphenyl)-1,3-propanedione (Nflll, Example 11), 1-(3-fluoro-
4-hydroxyphenyl)-2-bromo-3-(4-)
(lifluoromethylphenyl)-1,3-propanedione (Nl112.Example 12), 1-C4-((-)-2
-methylbutoxy)phenyl2-dibromo-3-(
4-chlorophenyl)-1,3-propanedione (Nf
l13゜Example 13), 1-(4-(-)-2-methylbutoxy)phenyl-2-bromo-3-(4-bromophenyl)-1,3-propanedione (Nl114
, Example 14), 1-(4-((-)-2-methylbutoxy)phenyl-2-dibromo-3-(3-bromo-4-methoxyphenyl)-1゜3-propanedione (
N (115, Example 15), 1-[3-fluoro-4-
((-)-2-methylbutoxy)phenyl-2-dibromo-3-(3-chloro-4-methoxyphenyl)-1
, 3-propanedione (No, 18. Example 1B),
1-(3-chloro-4-((-)-2-methylbutoxy)phenyl)-2-dibromo-3-(4-fluorophenyl)-1,3-propanedione (Nl117. Example 17), ■ -[3-chloro-4-((-)-2-methylbutoxy)phenyl-2-dibromo-3-(4-
trifluoromethylphenyl)-1゜3-propanedione (Nα18. Example 18), ■-[3-chloro-4-
<(-)-2-methylbutoxy)phenyl-2-dibromo-3-(3,4-dimethoxyphenyl)-1,3
-Propanedione (positive 19. Example 19), ■-[3-
Bromo-4i(-)-'2-methylbutoxy)phenyl-2-dibromo-3-(3,4-dichlorophenyl)
-1,3-propanedione (N1120. Example 20)
, 1-[3-bromo-4-((-)-2-methylbutoxy)phenyl-2-dibromo-3=(3-chloro-4
-ethoxyphenyl)-1゜3-propanedione (floor 2
1. Example 21), 1-[3-bromo-4-((-)-
2-methylbutoxy)phenyl-2-dibromo-3-
(3-Bromo-4-methoxyphenyl)-1,3-propanedione (Nα22. Example 22), 1-(4-(
(2s,3s)-2-chloro-3-methyl-1-butoxy)phenyl2-dibromo-3-(4-methquinphenyl)-1,3-propanedione (Nα23. Example 23), 1- [3-chloro-4-((2s,3s)-2
-rioo-3-1thyl-1-butoxy)phenyl2
-dibromo-3-(4-chlorophenyl)-1,3-7
"L'Opansion (Nα24. Example 24), 1-(3-
Chloro-4-((2s,3s)-2-chloro-3-methyl-1-butquine)phenyl-2-dibromo-3(4
-methoxyphenyl)-1,3-propanedione (Nα
25. Example 25), ■-[3-chloro-4-((2s
, 3s)-2-chloro-3-methyl-1-butoxy)phenyl)-2-dibromo-3-(3,4-dimethoxyphenyl)-1,3-propanedione (Nα26. Example 26), 1- (4-((2S,3S)-2-chloro-3-methyl-1-butoxy)phenyl-2-dibromo-3-(3-chloro-4-methoxyphenyl)-1,
3-propanedione (Nα27. Example 27), ■-[
3-chloro-4-((2s,3s)-2-chloro-3-
Methyl-1-butoxy)phenyl-2-dibromo-3
-(3-bromo-4-ethoxyphenyl)-1,3-propanedione (N[128°Example 28), 1-(
4-((2s,3s)-2-bromo-3-methyl-1-
butoxy)phenyl-2-dibromo-3-(3,5-
dimethoxyphenyl)-1,3-propanedione (N1
129. Example 29), 1-(4-((2s, 3s)
-2-bromo-3-methyl-1-butoxy)phenyl2-dibromo-3-(2,4-dichlorophenyl)-
1,3-propanedione (N[130, Example 30)
, 1-(4-((2s,3s)-2-bromo-3-methyl-1-butoxy)phenyl)-2-dibromo-3-
(4-mercaptomethoxyphenyl)-1,3-propanedione (N(L31. Example 31), 1-(4-((
2s, 3s) -2-bromo-3-methyl-1-butoxy)phenyl-2-dibromo-3-(3-fluoro-
4-methoxyphenyl)-1,3-propanedione (N
α32゜Example 32), ■-[3-chloro-4((2s
.

3s)-2-fluoro-3-methyl-1-butoxy)phenyl-2-dibromo-3-(3-chlorophenyl)
-1,3-propanedione (N1133゜Example 33)
, 1-[3-chloro-4-((2s.

3s) -2-fluoro-3-methyl-1-butoxy)
Phenyl-2-dibromo-3-(4-methoxyphenyl)-1,3-propanedione (Na34, Example 34
), 1-(3-bromo-4-((2s*3s) -2
-Fluoro-3-methyl-1-butoxy)phenyl-2-dibromo-3-(3-chloro-4-ethoxyphenyl)-1,3-propanedione (Tooth 35. Example 35) Margin table below - 1 Table -2 Table-3 Table-4 Table-5 Table-6 (Effects of the Invention) The compound of the present invention has a skeleton to which π-electron conjugated molecules are bonded via carbon.

Furthermore, since at least one Br group is bonded to this quaternary carbon, it is thought that a crystal structure is formed without the dipole moments of each π-electron conjugated molecule being canceled out due to steric hindrance with the aromatic ring.

Therefore, by adding a substituent that has an appropriate dipole moment, intramolecular resonance can be induced, and a large nonlinear susceptibility can be expected.

Furthermore, since this compound has a Br group in its molecule, this acts as a molecular orientation control group and can change the bulk structure of the crystal. That is, it is an effective functional substituent that can induce a non-centrosymmetric structure necessary for SHG activity.

Furthermore, compared to CT-type molecules such as MNA, the compound of the present invention does not have absorption in the long wavelength region, so that the compound is less likely to deteriorate due to absorption of the second harmonic.

The compound of the present invention has a high melting point, low sublimation property, and low water absorption, so it has excellent storage stability. It also has extremely high nonlinear susceptibility and excellent laser resistance. can be provided.

Therefore, it is effective for optical information and optical communications including wavelength conversion elements for semiconductor lasers.

[Brief explanation of drawings]

FIG. 1 is a schematic diagram showing a second harmonic generator used in an embodiment of the present invention. l: Q switch Nd; YAG laser - 2: Laser mirror for 10B4nm 3: Shutter 4: Sample (powder) 5: Condensing lens 6: Infrared cut filter 7: Polychromator 8: Multi-channel photodiode 9: MCPD drive circuit

Claims (1)

[Claims] (1) A nonlinear optical material characterized by containing a 1,3-diketone derivative represented by the following general formula [1]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [1] (In the formula, Y is Br or hydrogen, and the substituents R^1 may be different or the same, and are substituted with an amino group or a group having 1 to 12 carbon atoms. is an organic substituent selected from a substituted amino group, a cyclic amino group, an alkyl group, a halogen-substituted alkyl group, an alkoxy group, a halogen-substituted alkoxy group, and a mercaptoalkoxy group, where n indicates the number and is 1 to 1.
5, R^2 is the same organic substituent as R^1, and m indicates its number and is 0 to 5. A and B are cyclic organic groups and represent residues of aromatic hydrocarbons or heteroaromatic hydrocarbons. )