JPS63163827A - Organic nonlinear optical material - Google Patents

Abstract

PURPOSE:To obtain the titled material having an excellent nonlinearity and capable of generating effectively a multiplying wave by composing the titled material by a specific hydrazone compd. and a specific azido compd. or another compd. CONSTITUTION:The titled material is composed of the hydrazone compd. shown by formula I, and the azido compd. shown by formula II or the compd. shown by formula III. In the formulas, R1-R4 may be the same or the different with each other, and are each a nonsubstd. or a substd. heterocyclic ring group, etc., or hydrogen atom, but, R3 and R4 are not both hydrogen atom, R5-R8 may be the same or the different with each other, and are each a nonsubstd. or substd. heterocyclic ring, etc. or hydrogen atom, but R5 and R6 or R7 and R8 is not both hydrogen atom. Thus, the titled material has the excellent nonlinearity and can generate effectively the multiplying wave, and is applicable to the generation of higher harmonics and the fields of a high speed optical shutter and an optical bistability element, etc.

Description

[Detailed description of the invention] [Purpose of the invention] (Industrial application field) The present invention relates to a novel organic nonlinear optical material.

(Prior Art) Nonlinear optical effects are used to modulate the wavelength, phase, and amplitude of laser light, such as harmonic generation, optical switching, and optical mixing, and play an important role in information processing using light. As such nonlinear optical materials, many a-organic compounds have been discovered in recent years that have much larger nonlinear optical constants than conventional inorganic crystals and have excellent durability against optical damage.

As a review of these q-edge type optical materials, p.
“Non1inea” by J. Williams et al.
r 0pLIcalProperlLy of' Or
ganic and Polya+eric Mate
real “Afflerican Chemica”
15ociety 1983. A feature of the molecular structure of the q-machine nonlinear optical material mentioned here is that an electron-donating functional group and an electron-accepting functional group are bonded to both ends of a π-electron system such as a benzene ring.

However, in the above-mentioned molecular structure, due to the presence of an electric dipole in the ground state, a center-symmetric structure is formed upon crystallization, and there is a problem in that the large nonlinearity of one molecule is easily canceled out by the crystal as a whole.

Furthermore, when the spatial flooring of the π-electron system is expanded, nonlinearity increases, but on the other hand, the absorption band of the molecule itself overlaps with the wavelength of the fundamental wave or the harmonic, which results in hindering the efficient generation of the harmonic.

(Problems to be Solved by the Invention) The present invention has been made to solve the above conventional problems, and is an organic nonlinear optical material that exhibits excellent nonlinearity and can efficiently generate harmonics. This is what we are trying to provide.

[Structure of the Invention] (Means for Solving the Problems) The present invention provides a hydrazone compound represented by the following general formula (1), an azide compound represented by the following general formula (n), or the following general formula (III). ) is an organic nonlinear optical material characterized by being composed of a compound represented by:

However, R1 to R4 in the formula may be the same or different, and are each an unsubstituted or substituted heterocyclic group, an unsubstituted or substituted aryl group, an unsubstituted or substituted aralkyl group, an unsubstituted or substituted alkyl group, or Indicates a hydrogen atom. Note that the case where both R3 and R4 are hydrogen atoms is excluded.

However, R5 to RB in the formula may be the same or different, and are each an unsubstituted or substituted heterocyclic group, an unsubstituted or substituted aryl group, an unsubstituted or substituted aralkyl group, an unsubstituted or substituted alkyl group, or Indicates a hydrogen atom. Note that the case where R5, R6 or R7, R8 are both hydrogen atoms is excluded. Furthermore, R5 and R6 or R7 and R8 may form a hydrocarbon ring group or a polycyclic ring group.

However, R in the formula represents an electron-accepting group, and R represents an alkyl group.

Examples of the heterocyclic group introduced into the above general formula (I) or general formula (n) as R1-R8 include (i) a roll ring group, an indole ring group, an indoline ring group, an isoindole ring group,
Carbazole ring group, furan ring group, benzofuran ring group, thiophene ring group, pyrazole ring group, pyrazoline ring group, benzopyrazole ring group, imidazole ring group, imidacillin ring group, benzimidazole ring group, oxazole ring group, benzoxazole ring group , naphthoxazole ring group, oxazoline ring group, thiazole ring group, thiazoline ring group, benzothiazoline ring group, triazole ring group, benzotriazole ring group, oxadiazole ring group, thiadiazole ring group,
benzoxadiazole ring group, penzothiazole ring group, tetrazole ring group, pyridine ring group, quinoline ring group, acridine ring group, phenanthridine ring group, benzoquinoline ring group, naphthoquinoline ring group, bilane ring group, Benzopyran ring group, thiapyran ring group, pyridine ring group, pyrimidine ring group, pyrazine ring group, oxazine ring group, benzoxazine ring group, thiazine ring group, benzothiazine ring group, phenonethiazine ring group, diochitone ring group, triazine ring group , oxadiazine ring group, thiadiazine ring group, tetrazine ring group, benzofuran ring group, thiazole ring group, benzothiazole ring group, naphthothiazole ring group, selenazole ring group, benzoselenazole ring group, naphthoselenazole ring group, etc. Heterocyclic groups, ■ dialkylamino groups such as dimethylamino group, diethylamino group, dibutylamino group, methylethylamino group, methylbutylamino group, cyamylamino group,
; dialkylamino groups such as dibenzylamino group and diphenethylamino group; di-substituted amino groups such as diarylamino groups such as diphenylamino group, ditolylamino group and dixylylamino group; alkoxy groups (e.g. methoxy group, ethoxy group, propoxy group, butoxy group), aryloxy group (e.g. phenoxy group, naphthoxy group),
Alkyl group, nitro group, cyano group, hydroxy group, acetyl group, ester group (e.g. methyl ester group, ethyl ester group, phenyl ester group) or a substituted polycyclic group in which the group ① above is substituted with can be mentioned.

can be mentioned.

Examples of the aryl group introduced as R1-R8 into the above general formula (I) or general formula (n) include ■ phenyl group,
Naphthyl group, anthracene group, phenanthrene group, tetralin group, azulene group, biphenyl group, acenaphthylene group, acenaphthene group, fluorene group, triphenylene group, pyrene group, chrysene group, naphthalene group, bicene group, perylene group, benzopyrene group, rubicene group , coronene group,
Unsubstituted aryl group such as obalene group, ① dimethylamino group, diethylamino group 1. dialkylamino groups such as dibutylamino group, methylethylamino group, methylbutylamino group, cyamylamino group; dialkylamino groups such as dibenzylamino group, diphenethylamino group; diphenylamino group, ditolylamino group, dixylylamino group di-substituted amino groups such as diarylamino groups, alkoxy groups (e.g. methoxy, ethoxy, propoxy, butoxy), aryloxy groups (e.g. phenoxy, naphthoxy), alkyl groups, nitro groups, Examples include a cyano group, a hydroxy group, an acetyl group, an ester group (for example, a methyl ester group, an ethyl ester group, a phenyl ester group), or a substituted aryl group in which the group (2) above is substituted with a halogen.

Examples of the aralkyl group introduced into the above general formula (1) or general formula 1) as R1-R8 include benzyl group, phenethyl group, phenylpropyl group, phenylbutyl group,
unsubstituted aralkyl groups such as naphthylmethyl group and naphthylethyl group; ■ dialkylamino groups such as dimethylamino group, diethylamino group, dibutylamino group, methylethylamino group, methylbutylamino group, and cyamylamino group;
; dialkylamino groups such as dibenzylamino group and diphenethylamino group; di-substituted amino groups such as diarylamino groups such as diphenylamino group, ditolylamino group and dixylylamino group; alkoxy groups (e.g. methoxy group, ethoxy group, propoxy group, butoxy group), aryloxy group (e.g. phenoxy group, naphthoxy group),
Examples include an alkyl group, a nitro group, a cyano group, a hydroxy group, an acetyl group, an ester group (for example, a methyl ester group, an ethyl ester group, a phenyl ester group), or a substituted aralkyl group in which the above group (①) is substituted with a halogen. .

Examples of the alkyl group introduced as R1-R8 into the above general formula (1) or general formula (II) include ■methyl group,
Unsubstituted alkyl groups such as ethyl group, propyl group, isopropyl group, butyl group, pentyl group, hexyl group, ■ dimethylamino group, diethylamino group, dibutylamino group, methylethylamino group, methylbutylamino group, cyamylamino group, etc. dialkylamino groups; dialkylamino groups such as dibenzylamino groups and diphenethylamino groups; disubstituted amino groups such as diarylamino groups such as diphenylamino groups, ditolylamino groups, and dixylylamino groups; and alkoxy groups; For example, methoxy group, ethoxy group, propoxy group, butoxy group), aryloxy group (e.g. phenoxy group, naphthoxy group), nitro group, cyano group, hydroxy group, acetyl group, ester group (e.g. methyl ester group, ethyl ester group, (phenyl ester group) or a substituted alkyl group in which the group (2) above is substituted with a halogen.

Specific examples of the hydrazine compound represented by the above general formula (1) include those of the following structural formulas (1) to (20), and azine compounds represented by the above general formula (n). To specifically illustrate, the following (21) to
The structural formula (39) can be mentioned.

(n (2>(3n)

(4) (S”l
(6>wo(7) (y)('
I) (Ha) (u) (+2) (13)
(+4)(Is
) (+6) (1wa) C
18) (lily)
(22)(,+5)
04-) (2g)
(Koro) (27n)

(J(2Q) (3o)F(3,3) "Δ4) ' (3g) (3≦) (37)J (s8) Electron accepting property introduced as R9 in the above general formula (I[I) Examples of the group include a cyano group and a nitro group, and examples of the alkyl group introduced into the general formula (m) as RID include a methyl group, an ethyl group, a propyl group, a butyl group, etc. Specific examples of the general formula (III) include:
Examples include those having the following structural formulas (40) to (49).

--(A?1 11-c Buddha) =-C4Q -1-(4'7) ---(4 back) ---(4"l) (Function) According to the present invention, "-- In the molecular structure of general formula (1) or (II), the π-electron system of the hydrazone skeleton or azine skeleton is spatially expanded by the functional group RI-R4 or R5-R8, and R1 to R4% or R5- The difference in electron-donating or electron-accepting properties of R8 causes asymmetry in the movement of π electrons with respect to the electric field of the fundamental wave, and nonlinear polarization is excited to generate high-frequency waves. Moreover, the above general formula (III
), the methylenedioxy group bonded to the benzene ring is electron-donating, and the heptad-accepting group represented by R9, the king of the benzene ring, constitutes a π-electron system extending between these kings. , this asymmetric π-electron system becomes the origin of the nonlinear response and can generate harmonics. Note that the ester group formed by bonding an alkyl group to general formula (III) has a function of determining the crystal structure.

(Example of the invention) Examples of the present invention will be described in detail below.

The above structural formula Na8.9.10.11%+4.20.
21° 22.40~42.44~47.49 161!
Microcrystals of the compound were prepared, and these microcrystals were finely ground in an agate mortar to prepare powders with uniform particle sizes. These powders were then sandwiched between a pair of glass slides to form a sample. In addition, KDP (potassium dihydrogen phosphate) TLT crystal was used as a reference sample.

Next, an experiment was conducted on second harmonic generation (5HG) for each of the samples using the second harmonic generation and detection device shown in the drawings.

That is, wavelength (λ) -1,06 μm, output 200 ta
J, pulse width 20 ns, pulse repetition frequency 5 Hz
A fundamental wave was emitted from a Q-switched Nd-YAG laser I, which was split into two beams by a beam splitter 2, and one beam was irradiated onto the sample 3 described above, and the other beam was irradiated onto the reference sample 4 described above. . Since the reflected light from the sample 3 also contained a fundamental wave, the light was focused by a condenser lens 5, and then the fundamental wave component was absorbed and removed by a sulfuric acid aqueous solution filter 6I. Since the transmitted light from the reference sample 4 also contained a fundamental wave, the fundamental wave component was similarly absorbed and removed by the sulfuric acid aqueous solution filter 82. These filters 6, . The light from 82 is converted into a voltage signal by the photoelectron multiplier -7? The intensity of was detected.

In such detection, the A/B mode of the boxcar product M9 (A mode: a mode in which a voltage signal corresponding to the sample 3 is input, B mode: a mode in which a voltage signal corresponding to the reference sample 4 is input manually) By displaying the signal ratio from the reference sample 4 and the sample 3 using the mode (), it is possible to perform measurements that are not affected by the intensity of the laser beam.

The SHG intensity of each sample obtained in the above experiment is shown in the table below. However, the SHG intensity in the table is a value relative to KDP used as a reference sample.

As is clear from the above table, all the compounds of the present invention are SHG
is expected to occur and have excellent performance.

[Effects of the Invention] As detailed below, the nonlinear optical material of the present invention exhibits excellent nonlinearity and can efficiently generate harmonics, and is useful for high-speed optical shutters including harmonic generation. , it can be applied to the field of optical bistable devices, etc., and has many remarkable effects.

[Brief explanation of the drawing]

The drawing is a schematic diagram showing a second harmonic generation and detection device used in an embodiment of the present invention. ■・・・Q switch N d-Y AG laser, 2...
・Beam splitter, 3...sample, 4...reference sample, 60.62...copper sulfate aqueous solution filter, ? ,,7
2...Photomultiplier tube, 81.82...Amplifier, 9.
...Boxcar integrator.

Claims (1)

[Claims] A hydrazone compound represented by the following general formula (I),
An organic nonlinear optical material comprising an azide compound represented by the following general formula (II) or a compound represented by the following general formula (III). ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) However, R_1 to R_4 in the formula may be the same or different, and each represents an unsubstituted or substituted heterocyclic group or an unsubstituted or substituted aryl group. , unsubstituted or substituted aralkyl group, unsubstituted or substituted alkyl group, or hydrogen atom. Note that the case where both R_3 and R_4 are hydrogen atoms is excluded. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(II) However, R_5 to R_8 in the formula may be the same or different, and each represents an unsubstituted or substituted heterocyclic group or an unsubstituted or substituted aryl group. , unsubstituted or substituted aralkyl group, unsubstituted or substituted alkyl group, or hydrogen atom. Note that the case where R_5, R_6 or R_7, R_8 are both hydrogen atoms is excluded. Also, R_5 and R_8 or R_
7 and R_8 may form a hydrocarbon ring group or a heterocyclic group. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(III) However, R_9 in the formula represents an electron-accepting group, and R_1_0 represents an alkyl group.