JPH0383026A - Non-linear optical element, manufacture thereof, optical apparatus containing the same and compound having non-linear optical nature - Google Patents

Abstract

PURPOSE: To obtain an optical element having nonlinear optical properties consisting of a light-transmitting or reflecting base body by forming a single layer having such a structure that two nonlinear optical(NLO) compds. selected from two compds. each having an electronic vector and salts of these compds. are alternately arranged to have the electronic vectors in one direction. CONSTITUTION: A single layer is formed in such a manner that two NLO compds. selected from two compds. each having an electronic vector, namely compds. expressed by formula I, II and salts of these are alternately arranged. However, two compds. in the single layer are arranged to have the electronic vectors in one direction. In formula I, R<2> is a nonhydrophilic aliphatic group having 10 to 24 carbon atoms containing alicyclic groups and oxa- or thia-substitution, D<1> is -NX-, wherein X is H or 1 to 4C alkyl group, Ph is a p-phenylene group, R<2> to R<6> are H or 1 to 4C alkyl groups, n is an integer 1 to 10, A<1> is NO2 , etc., A<2> is H or A<1> . In formula II, A<3> is the same as A<1> in formula I, m is an integer 1 to 4, D<2> is same as D1 in formula I, R<7> to R<11> are H or 1 to 4C alkyl groups, p is an integer 1 to 10, A<4> is same as A<2> is formula I, and R<12> is the same as R<1> in formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a nonlinear optical (IIon-1ine) method comprising alternating monolayers of two related compounds.
The present invention relates to an optical element having the following properties: ar optical (hereinafter referred to as NLO).

According to the present invention, two compounds each having an electron vector, namely the formula: %formula% (1) [wherein R1 optionally contains an alicyclic group and optionally oxa-substituted or thia-substituted is a substituted non-hydrophilic C8°-24 aliphatic group; Dl is -NX-1-NH-NX- or -N(O
X)- (where X is H or C, an alkyl group); Ph is a P-phenylene group; R8 to R1
are each independently H or C1-4 alkyl group:
n is an integer from 1 to 10: A1 is No, CN or C
00Y (However, Y is H or C1□ alkyl group)
and A2 is H or a group defined for A1]
"First NLO compound" selected from compounds and salts thereof and formula: %Formula% () [wherein A3 is the group defined for A' in formula (1); m is 1 to 4 is an integer; D2 is D in formula (I)
Ph is a P-phenylene group: R'' to 1 (11 are each independently H or CZ-* alkyl group; p is an integer from 1 to 10; A4 is Atom or group as defined for A2 in formula (I); and R12 is a group as defined for R1 in formula (1)] and salts thereof.
"second NLO compounds", alternating layers, provided that in these first layers these two compounds are arranged such that they have electron vectors in the same direction. As used herein, the term "non-ligophilic" means not substituted with hydrophilic substituents such as carboxylate, sulfonate, phosphonate and hydroxyl groups.

-NLOhiA in the first NLO compound, R1 optionally contains (but more preferably does not contain) an alicyclic group, 10 to 16;
More preferably long chain aliphatic groups containing from 12 to 16 carbon atoms are preferred; some variation in chain length within these preferred limits has little effect on the nonlinear optical properties of the compound. It is considered to be a waste. Furthermore, the aliphatic chain has no branches or at most one or two branches, and each branch has one branch.
It is preferable that the carbon has only one or two carbon atoms.

Alicyclic groups when included in R1 may suitably contain 5 to 12, preferably 5 to 7 carbon atoms.

R1 may be substituted by 1(I) or more heteroatoms, especially oxygen or sulfur atoms.

If R1 is substituted by one or more heteroatoms, it is preferred that there are not more than 1 peteroatom per 12 carbon atoms in the chain, the group represented by R1 being a halogen atom. It may have non-hydrophilic substituents such as, but preferably it is a hydrocarbon group.

Examples of groups represented by R1 are decyl, undecyl,
dodecyl (lauryl), heptadecyl (margaryl),
These are octadecyl (stearyl), nonadecyl, eicosanyl (araxyl), heneicosanyl, docosanyl (behenyl), tricosanyl, and tetracosanyl (lignoseryl) groups.

Further examples of groups represented by R1 are lO-eicosanyl, 9,12-octadecagenyl (lylyl) and 6
-hexyloxyhexyl group.

A preferred D1 group is an -NX- group as defined above, preferably one in which X is H or a methyl group.

Preferred R1-01- includes N-methyl-N-decylamino and N-methyl-N-dodecylamino groups.

R2 to R6 are preferably each independently H or a methyl group, more preferably R2 and R' are each a methyl group and the remainder is H. In that case, the two methyl groups are preferably in trans position with respect to each other.

It is preferable that n is 1-4.

A8 is preferably a group other than H in the defined range. When tL or A3 is cooy in the defined range and Y represents an 01-4 alkyl group, it is preferably a methyl group, but More preferably, Y is H. Preferred examples of Ai and A2 are carboxyl and CN groups, and a combination of these two groups is particularly preferred. The salt of the compound of formula (I) is a salt of a carboxyl group. Examples include metal salts or salts in which the cation contains a tetravalent nitrogen atom and/or acid addition salts of basic nitrogen atoms.

If the cation of the salt is a metal, it is preferably divalent, the preferred metal being cadmium.

These are barium, lead and calcium.

Other suitable salt cationic metals are manganese and zinc.

Includes magnesium and strontium.

When the cation of the salt is one containing a tetravalent nitrogen atom, it may be an ammonium cation such as NH, mono-, di- or tri-substituted ammonium or quaternary ammonium.

Other suitable salt cations containing tetravalent nitrogen atoms include bis(ammonium) cations such as alkylene- and alkenylene-diammonium, guanidinium, biguanidinium and amidinium.

The tetravalent nitrogen atom in such cations may have substituents other than hydrogen; suitable such substituents include alkyl groups such as methyl, ethyl, lauryl, cetyl, stearyl; aryl groups such as phenyl; and cycloalkyl groups such as cyclohexyl.

These substituents may themselves be substituted, for example C1-1 alkyl substituents such as tolyl, C1- such as anisyl and ethoxyethyl groups.

Examples include alkoxy substituted products, halogen substituted products such as chlorphenyl group, and hydroxy substituted products such as hydroxyethyl group. Particular examples of suitable groups are NH,,N(C
)I,)N (C2H40H)4, N (CH3)3
(C Engineering, H,,),)! 3N-C, H4-NH3.

When the salt is an acid addition salt, it may be a hydrohalide, sulfate, organylsulfonate salt or phosphate.

A specific example of a first NLO compound is 1-(4-N-
Methyl-N-dodecylaminophenyl)-3,8-dimethyl-10-carboxyl-1o-cyanodeca-1,3
, 5,7,9-pentaene and its calcium and cadmium salts.

Other specific examples of first NLO compounds further include 1-(4-N-methyl-N-dobcyaminophenyl)-
3-methyl-8-carboxy-octa-1,3,5,7
-tetraene [compound (2)); 1- (4-N-methyl-N-dodecylaminophenyl)-3,&-dimethyl-10-nitrodecar 1.3,5,7.9-pentaene [compound (3)] ; 1-(4-N-methyl-N-decylaminophenyl)-
6-dianohexa-1,3,5-triene: 1-(4-N-methyl-N-dodecylaminophenyl)-6-carboxy-6-cyasohexer 1.3.5-
Triene [compound (4)); 1-(4-N-methyl-N
-decylaminophenyl)-6-diatsuhexer i, 3
．． 5-triene; 1-(4-methyl-N-tetracosanylaminophenyl)-6-carboxy-6-cyanohexa-1,3,5-
Triene;
-4-dodecylcyclohexylaminophenyl)-20
-carboxy-20-cyanoeicosa-1,3,5,7
,9゜11.13,15,17,19~decaene;1-
(4-N-methyl-N-4-dodecylcyclohexylaminophenyl)-6-carpoxy 6-cyano 3,4
-trans-dimethylhexa-1,3,5-triene; 1-(4-N-methyl-N-6-hexyloxyhexylaminophenyl)-3,8-dimethyl-10-methoxycarbonyldeca-1° 3.5,7.9-pentaene; 1-(4-N-methyl-N-6-hexyloxyhexylaminophenyl)-3,8-dimethyl-10-cyanodeca-1,3,5,7,9 -Pentaene; 1-(4-N-methyl-N-dodecylaminophenyl)-3,13-dimethyl-10-methoxycarbonyldeca-1,3,5,7,9-pentaene: 1-(4-N- Methyl-N-dobcylacybanophenyl)
-3,8-dimethyl-10-carboxydodeca-1,
3,5,7,9,11-hexaene; 1- (4-N-
methyl-N-dodecylaminophenyl)-3,8-dimethyl-10-carboxydeca-1,3,5,7,9-pentaene: 1-(4-N-methyl-N-dodecylaminophenyl)-3, 8-dimethyl-10-carboxy-1
0-cyanodeca-1,3,5,7,9-pentaene [compound (5)); 1-(1-N-methyl-N-dodecylaminophenyl)
-2,9-dimethyl-10-carboxy-10-cyanodeca-1,3,5,7,9-pentaene; 1-(4-N-methyl-N-dodecylaminophenyl)-3,8-dimethyl-10 , 10-dicarboxydeca-1,3,5,7,9-pentaene; 1- (4-N-
Methyl-N-dodecylaminophenyl)-3,8-dimethyl-10-carboxy-10-nitrodeca-1,3,
5,7,9-pentaene; 1-(4-N-methyl-N-dodecylaminophenyl)-3-propyl-8-methyl-10-carboxy-1
0-cyanodeca-1,3,5,7,9-pentaene; and 1-(4-N-methyl-N-dodecylaminophenyl)-1,3,8-trimethyl-10-carboxy-10
-cyanodeca-1,3,5,7,9-pentaene; and salts thereof.

The first NLO compound is non-centrosymmetric along the long axis of its molecule because the A1 and optionally A1 groups are each electron-withdrawing and the RL-o L- group is electron-donating. and is substantially polarizable.

Therefore, the molecule of the compound has R1-D along its axis.
It can be expressed as an electron vector from the ``- group toward the A1 group and possibly the A2 group.

The first NLO compound is R1-Dl-P of the molecule of formula (I)
h-CR'' molecular moiety and the precursors of the remaining portions of the molecule of formula (I), for example by Witzteig reaction or any conventional method for C-C bond formation.
〇Can be manufactured by forming a bond.

It will be clear to those skilled in the art that some of the groups D1, A1 and A2 may give rise to undesirable side reactions; such groups can be protected during the reaction process by conventional leaving protecting groups; After the protecting group has served its purpose, it is removed from the reaction product by conventional methods. Alternatively, the precursor can include a precursor of the final desired group, which will be converted into the desired group in the reaction product, thus for example D1= NH can be protected by conventional N-protecting groups and Ai or A"
Suitable precursors for =C0OH may include aldehyde precursors of the C0OH group.

The compounds of formula (1) can be salified by conventional methods or any carboxyl groups can be esterified by conventional methods.

In the second NLO compound, A1 is C00Y as defined for A1 in the first NLO compound of formula (1).
It is particularly preferred if (independently of A1) that m is 2 when Y is an 01-4 alkyl group.

Preferred D2 includes -NX- as defined for Dl in formula (I) (independently of Di), with X preferably being H or methyl.

Preferred A'-(CH,), -D''- include N-2-carboxyethyl-N-methylamino group and N-4-carboxybutyl-N-methylamino group.

R7 to Rtt are each independently preferably H or a methyl group, more preferably R7 and Hll
are each methyl and the remaining groups are H. In this case, the two methyl groups are preferably in trans position with respect to each other.

It is preferable that p is 1-4.

Preferably A4 is a defined group other than H.

Examples of preferred groups for 1 and A4 are carboxyl groups and CN groups, with CN groups being particularly preferred.

R12 is preferably a long-chain aliphatic group of the same type and containing the same components and the same number of carbon atoms as the group previously shown as preferred for R1 in formula (1), provided that it is selected independently of R1. .

The preferred combinations of groups indicated for A4 and R12 are particularly preferred.

The salt of the second NLO compound of formula (II) can be a salt of a carboxyl group, and the salt can be a metal salt and a salt in which the cation contains a tetravalent nitrogen atom and/or an acid addition salt of a basic nitrogen atom. include.

Suitable and preferred salts are similar to the preferred salts mentioned for the salt of the first NLO compound of formula (1).

A specific example of a second NLO compound is 1-(4-N-methyl-N-2-carboxyethylaminophenyl)-3,8
-dimethyl-10-dodecyloxycarbonyl-10-
Includes cyanodeca-1,3,5,7,9-pentaene and its calcium and cadmium salts.

Other specific examples of second NLO compounds further include:

1- (4-N-methyl-N-2-carboxyethylaminophenyl)-3-methyl-8-decyloxycarbonylocta-1,3,5,7-tetraene; 1- (4-N-methyl-N -2-carboxyethylaminophenyl)-3,8-dimethyl-10-dodecyloxycarbonyl-10-nitrode-1,3,5,7,
9-pentaene; 1-(4-N-methyl-N-carboxymethylaminophenyl)-6-dianohexa-1,
3,5-triene; 1- (4-N-methyl-N-2-
carboxyethylaminophenyl)-6-decyloxycarbonyl-6-cyanohexa-1,3,5-triene: 1-(4-N-methyl-N-carboxymethylaminophenyl)-6-dianohexa-1,3,5 -triene; 1- (4-N-methyl-N-4-carboxybutylaminophenyl)-6-dodecyloxycarbonyl-6
-Cyanohexa-1,3,5-triene: 1- (4-N-methyl-N-4-carboxybutylaminophenyl)-6-dodecyloxynitronyl-6-
Nitrohexer 1.3.5-triene; 1-(4-N-methyl-N-2-cyanoethylaminophenyl)-20-tetracosanyloxycarbonyl-
20-cyanoeicosa-1,3,5,7,9,11,1
3,15,17,19-decaene; 1-(4-N-methyl-N-2-cyanoethylaminophenyl)-6-tetracosanyloxycarbonyl-6-cyano-3,4-
trans-dimethylhexa-1,3,5-triene; 1
-(4-N-methyl-N-2-nitroethylaminophenyl)-3,8-dimethyl-10-dodecyloxycarbonyl-10-methoxycarbonyldeca-1,3,5,
7,9-pentaene; 1-(4-N-methyl-N-2
-nitroethylaminophenyl)-3,8-dimethyl-
10-dodecyloxycarbonyl-10-cyanodeca-
1,3,5,7,9-pentaene; 1-(4-N-methyl-N-2-carboxyethylaminophenyl)-3,
8-dimethyl-10-dodecyloxycarbonyl-10
-methoxycarbonyldeca-1,3,5,7,9-pentaene; 1- (4-N-methyl-N-2-carboxyethylaminophenyl)-3,8-dimethyl-10-
Dodecyloxycarbonyl dodeca-l.

3.5,7,9.11-Hexaene: 1-(4-N-methyl-N-2-carboxyethylaminophenyl)-3,8-dimethyl-10-dodecyloxycarbonyl-10-cyanodeca-1,3 ,5,7,9
-Pentaene; 1-(4-N-methyl-N-2-carboxyethylaminophenyl)-3,8-dimethyl-10
-dodecyloxycarbonyl-10-cyanodeca-1,
3,5,7,9-pentaene; 1-(4-N-methyl-
N-2-carboxyethylaminophenyl)-2,9-
Dimethyl-10-dodecyloxycarbonyl-10-cyanodeca-1,3,5,7,9-pentaene; 1- (
4-N-methyl-N-2-carboxyethylaminophenyl)-3,8-dimethyl-10-methoxycarbonyl-10-dodecyloxycarbonyldeca-1,3,5,
7,9-pentaene; 1-(4-N-methyl-N-2
-carboxyethylaminophenyl)-3,8-dimethyl-10-dodecyloxycarbonyl-10-nitrodeca-1,3,5,7,9-pentaene;
-methyl-N-2-carboxyethylaminophenyl)
-3-propyl-8-methyl-10-dodecyloxycarbonyl-10-cyanodeca-1,3,5,7,9-pentaene; and 1- (4-N-methyl-N-2-carboxyethylaminophenyl) -1,3,8-trimethyl-10-dodecyloxycarbonyl-10-cyanodeca-1,3,5,7,9-pentaene; and salts thereof.

The second NL○ compound is non-centrosymmetric along the long axis of its molecule and substantially polarizable because the carboxylate group is electron-withdrawing and the substituted amino group is electron-donating. be. The molecule of the compound can therefore be represented as an electron vector directed from the substituted amino group toward the carboxylate group along this long axis.

The second NLO compound can be prepared in exactly the same way as the first NLO compound (as described above) and under the same conditions and reservation of freedom of choice.

Due to the inherent properties of the second and second NLO compounds, they can form alternating monolayers (alternating monolayers) of NLO coatings.
the monolayers) are arranged in the same manner.

This means that the vectors along the long axis of the molecules are substantially parallel and in the same direction.

In the NLO coating, the long chain aliphatic group (R1) in the first NLO compound is replaced by the long chain aliphatic group (R”) in the second NLO compound.
), i.e., the electron vectors of both these compounds are in the same direction. The overall effect would therefore be for the NL○ coating to be non-centrosymmetric along the axis perpendicular to the surface of the coating.

In a particularly preferred class of NL○ elements, NL
The O coating consists of two NLO compounds: 1-(4-N-methyl-dodecylaminophenyl)-3,8-dimethyl-1
0-carboxyl-10-cyanodeca-1,3,5,7
, 9-pentaene (compound ■) and 1-(4-N-methyl-N-2-carboxyethylaminophenyl)-3,
8-dimethyl-10-cyano-10-dodecyloxycarbonyldeca-1,3,5,7゜9-pentaene (compound ■) - which independently of each other in the form of the free acid or their cadmium or calcium salts or Consists of alternating layers of - present as methyl esters.

If the support is optically transparent at the wavelength of light to be used, the support may be provided with a first and a second NLO on its outer surface.
It can be in the form of an optical waveguide with a coating of alternating monolayers of compounds.

Using this type of optical element, the optical signal passing along the waveguide is evanescent wave (evanescent wave) that extends into the surface NL○ coating.
(scent waves) interact with the NLO coating to produce nonlinear optical effects.

Examples of suitable materials for supports in the form of waveguides are glass,
It can be in the form of plates or discs that can form such NLO coatings on both lithium niobate and nitride surfaces on silicon oxide. With this type of optical element, nonlinear optical effects can be induced in the transverse direction of the support and coating.
It can be obtained by illumination. Suitable supports for such types of optical elements include glass and poly(methyl methacrylate) (PMMA).

If the support is optically reflective, it advantageously has a flat reflective surface on which the NLO coating of the invention can be formed, so that the optical signal is transmitted immediately before contact with the reflective surface. Examples of suitable materials for reflective supports include aluminum, silver, or on supporting substrates such as glass, silica, quartz or poly(methyl methacrylate). It is a thin film of folded aluminum or silver. When using this type of optical element, there is one reference (Stegman et al., Appl. Phys.
Lett, 41(10) 906.1982;
5 and et al., pp1.0ptics 21 (22
), 3993, 1982], efficient nonlinear action can be achieved by exciting the so-called "surface plasmon" system.

The optical element of the present invention is Langmuir-Projet (La
It can be manufactured by the ngmuir-Blodgett method.

Therefore, according to a second aspect of the invention, the surface of a light-transmissive or reflective support is introduced into a liquid through a first surface supporting a surface monolayer of a first NLO compound; A method of making an optical element with nonlinear optical properties is provided, which comprises withdrawing from the liquid through a second surface supporting a surface layer of two NLO compounds.

Of course, this manufacturing method can also be carried out by reversing the steps.

The liquid used in the second aspect of the invention, hereinafter referred to as "sub-phase", is preferably an aqueous medium. Formation of a monolayer on the support is achieved in conventional manner by adjusting the surface area by means of a movable dam in a Langmuir trough.

Various types of optical elements according to the first invention can produce secondary nonlinear optical effects in various ways in various optical devices.

Therefore, according to the third aspect of the present invention, there is provided an optical device containing the NLO optical element according to the first aspect of the present invention.

An example of an optical device according to the invention consists of a support in the form of an optically transparent waveguide with an intimate coating formed by a number of alternating monolayers of first and second NLO compounds. a first surface (bottom) coating of silicon nitride having an optical element and forming a flat-surfaced waveguide and a second surface consisting of alternating monolayers of a first and second NLO compound; (Top) Consists of a silicon oxide plate with NLO coating.

In operation of the optical device, a first optical signal is conducted through the waveguide (in the plane of the waveguide).

This first optical signal interacts with the NLO coating by means of a vanishing wave that extends through the coating. This interaction generates a second optical signal at a second harmonic frequency with respect to the first optical signal, which can be detected in the combined optical signal leaving the waveguide.

Another optical device according to the invention will be described with reference to FIGS. 1 and 2.

FIG. 1 is a plan view of the optical device, and FIG. 2 is a top view of the optical device.
It is a sectional view taken along the XY line of the figure.

In this optical device, the optical element is mounted on a glass support 4.
and two optically transparent strip-shaped (3 tripa) waveguides 6 and 8 present in its upper surface area 5.

These striped waveguides 6 and 8 are formed in the desired pattern by well-known ion exchange or ion bombardment techniques and run exactly parallel (i.e. a few micrometers (typical) over the central portion of their length). 2-5 for
．． ) are arranged so that they run separated from each other at intervals of ).

The surface of the support 4 is coated with an NLO coating 9 of alternating monolayers of first and second NLO compounds. A pair of electrodes 10 and 12 connected to a power source (not shown) are arranged such that one electrode 10 is located above the striped waveguide 6 and the other electrode 12 is located below the waveguide 6. be done.

In operation, an optical signal is passed through the first waveguide 6 from A to B and a voltage is applied across these two electrodes. This changes the refractive index of the NLO coating by direct current (d, c,) electro-optical effect (Pockels effect) and thus changes the propagation constant of the first waveguide 6.

By suitably adjusting the applied voltage, the propagation constant of the first waveguide 6 can be adjusted such that the optical signal passing through this waveguide 6 is coupled into the second waveguide 8, and generating a second optical signal emerging from the device.

The optical element according to the first invention can be used in other known types of optical devices incorporating the optical element.
LO coatings, such as lithium niobate coatings, can be
It can be used by replacing the LO coating.

Next, the present invention will be further explained with reference to production examples of NLO compounds and examples of optical elements. In the following description, all parts and percentages are by weight unless otherwise indicated.

N-methyl-N-laurylaniline (110g), 4
0% formalin I solution (30g), triphenylphosphine (to4.8g), potassium iodide (66.4g),
Water (8a+Q), glacial acetic acid (80g) and chloroform (
4-(N-methyl-N-laurylamino)benzyltriphenylphosphonium iodite (compound a
) was manufactured. The solution was then washed in water and evaporated to give an oil, which was slurried in ether to form a precipitate of compound a (yield 298 g; 76.8% of theory), octa-2 ,4,6-dorien-2
,7-dial (compound b) was prepared using 2-oxopropanal dimethyl acetal (117 mfl) and toluene (3 mfl).
0On+Q) were stirred together at 50℃ and 8
Prepared by adding 0% sodium hydride (28.4 g) in small portions over 30 minutes. The mixture was then held at 50°C for 1 hour and then at 60°C for 1 hour before being acidified with 2N sulfuric acid.

Separate the toluene layer, wash with water and bring the temperature to 20°C.
When the mixture was adjusted, a precipitate of the compound was formed.

Compound a and compound A were then dimethylformamide (
100+*I2) at 20-25°C with stirring together.

Sodium methoxide (0.5 g of sodium in 150 methanol) was added dropwise until the ratio of starting material to product no longer decreased. After stirring for a further hour, the mixture was diluted with water (200+a12) and extracted with toluene.

The organic extract was dried, dissolved in chloroform and eluted on silica gel with toluene to give compound C. Compound C was then stirred with acetamide, ammonium acetate, cyanoacetic acid, glacial acetic acid and hexane at 60-65°C under reflux conditions for 4 hours.

After cooling to 20°C, the solid was filtered off, extracted with hot chloroform, washed with water and dried. The product was eluted on silica gel with toluene.

One fraction that slowly came off the column was collected and extracted with ethanol. When the solvent is evaporated, the metal compound 1 0.2
2 g (yield 22%) was obtained.

Compounds (2) to 5) described above were also produced in the same manner.

Furthermore, the remaining specific compounds of the first NLO compound described above were also produced in the same manner.

(II) Diltriphenylphosphonium iodite (compound d
) is N-(2-carboxyethyl)-N-methylaniline (25.06 g; 0.14 mol), 40% formaldehyde solution (10.5 g; 0.14 mol), triphenylphosphine (36.68 g; 0.14 mol)
, potassium iodide (23,24 g; 0.14 mol),
It was prepared by stirring a mixture of acetic acid (27 tQ) and chloroform (100 mQ) at room temperature for 5 days.

The resulting mixture was poured into ether to obtain an oily residue,
This was treated with ether to give a white solid.

The aldehyde compound (compound e) was prepared by diluting a 1M ethanolic sodium ethoxide solution (14 m former 0.14 mol) into octa-2,4,6 mol in dimethylformamide (50 mA).
-Doriene-2,7-dial (compound b, 1.15
g; 0.007 mol) and compound d (4.1 g;
0.007 mol) to a stirred suspension, the reaction occurred immediately to give an orange solution. This was poured into condensate water (200n+A) stirred for 1 hour at room temperature and acidified with hydrochloric acid.

The orange tarry precipitate resulting from acidification was extracted into dichloromethane. Wash this extract with water.

Dry over magnesium sulphate, evaporate to dryness under reduced pressure and then purify by flash chromatography (silica/dichloromethane).

Then piperidine (2 mQ) was added to n-dodecylcyanoacetate (1,27 g; 0.005 mol) and compound a.
(1,7 g; o, oos mol) was added to the mixture. The color of the mixture changed from dark orange to purple.

The mixture was poured into water, acidified with hydrochloric acid and extracted with dichloromethane. The extracts were washed with water and dried over magnesium sulfate. After evaporation to dryness under reduced pressure, the oily product was purified by flash chromatography (silica/ether-ethanol (4:1)) to yield a dark purple solid (compound ■, section 6.2; yield 7%). Ta.

Melting point: 1Q9-111°C λwax (ethanol): 525 nm Mass hectare = M/z 574 (M+) The remaining specific compounds of the second NLO compound described above were produced in the same manner.

The aqueous sub-phase consisted of a 1.0 mmolar solution of calcium acetate in water with P)l 6.5 held in a Langmuir trough.
se) on the surface of the hinge valve (a 1eaf spring
It was separated by a flexible PTFE floating barrier (hereinafter referred to as floating wall) containing a valve.

This hinge valve operates in such a way that the glass plate can be moved through the floating wall while being partially immersed in the subphase, yet without causing contact between the surface layers on either side of the floating wall.

In this way, glass plates can be introduced into the subphase on one side of the floating wall and removed from the subphase on the other side of the floating wall.

The floating wall is flexible so that equal surface pressure can be maintained on both sides of the wall.

The surface layer of the "first NLO compound" (Compound I above) is 1.0-1-7L/1L of compound 1 in chloroform.
Solution II was formed by slowly dropping it from a microsyringe onto the surface of the subphase on the first side (on the side) of the floating wall. A similar method was performed on the second side (side 2) of the floating wall with the "second NLO compound".

The solvent from each solution is evaporated and the surface pressure on both sides of the floating wall is increased by the movement of the adjustable floating wall in the trough.
6 mN/m and 26+*N during this immersion step.
/Holded by Peng.

The glass sheets, precleaned by ultrasonic cleaning in chloroform and methanol, immersed in sodium hydroxide for 24 hours, and dried, were made hydrophobic by exposing them to hexamethyldisilazane vapor for 424 hours.

The plate was then dipped into the subphase at a rate of 1 cm/min on side 1 of the trough, and a monolayer of compound 1 was deposited in a hydrophobic manner. The plate was then moved from side 1 to side 2 of the floating wall through a 1-hinged valve while immersed in the Misubphase.

This sliding plate is then 1.0 cIl from side 2 of the trough.
It was removed at a speed of 1 minute, during which time a monolayer of Compound II was folded onto the monolayer of Compound I in a hydrophobic manner. Insertion of this flat plate into side 1, movement through the 1-hinged valve, and removal from side 2 were repeated.

This iterative operation built up a thicker coating of alternating monolayers of Compound I and Compound H over the entire surface of the plate passed through the subphase.

Substantially all of the Compound I and Compound II molecules in the coating had vectors in the same direction and were oriented in parallel with added nonlinear optical coefficients.

The resulting optical elements (hereinafter referred to as 'OA1' and 'OA2') were coated with two and eight monolayers of Compound I and Compound II, respectively, arranged alternately on both surfaces of a flat glass plate. It consisted of a glass support.

Optical elements coated in alternating monolayers with any two of the other specific examples of the first and second NLO compounds described above were similarly produced.

Using the optical elements described in Example 1, their NLO characteristics were confirmed in the following manner.

Light beam from Nd:YAG pulse laser (wavelength 1.06
4 nm; pulse time Ion seconds: repetition rate 10 Hz) was passed through the glass flat plate and the NLO coating in the vertical direction.

The intensity of the emitted light beam at the second harmonic (wavelength 532 naa) generated while passing through the optical element is equal to the fundamental wavelength (
After filtering the transmitted light at 1,064 nm), measurements were taken using a multiplier phototube. After calibrating against the second harmonic generated by a reference test using a quartz plate of 2+u+, the calculated value of the second-order NLO coefficient Khi (2) OA
1 knee) itelt1.1.5X10-"C'J-"
C'A IJ, OA 2 Nitsuite Lt, 4.4X10
-"C'J-" Tea Tsuta, the average molecular secondary electron polarizability at wavelength 1, 064 tm is from Khi (1) to OAI
For 5.6X10-”C'J Mi 2μm21113
(1,5X10-”a1/esu), 1.7×10-”C3J-”m” for OA 2 (4,5X 1
0-''Cm3/esu), respectively. The difference between these numbers may be primarily due to the reduced degree of molecular alignment in thicker films.

[Brief explanation of drawings]

The drawings show one embodiment of the optical device according to the present invention, and FIG. 1 is a plan view of the optical device, and FIG.
It is a sectional view on the Y line. 4... Glass support: 5... Upper surface area of said support: 6 and 8... Light-transparent waveguide; 9... NLO coating; 1o and 12... Pair of electrodes. Engraving of drawings (no changes in content) Jun/Z Procedural amendment (voluntary) October 24, 1999

Claims (1)

[Claims] 1. Two compounds each having an electron vector, that is, the formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R^1 optionally includes an alicyclic group] and optionally oxa- or thia-substituted non-hydrophilic C_1_0_-_2
_4 is an aliphatic group; D^1 is -NX-, -NH-NX
- or -N(OX)- (where X is H or C_1_-_
Ph is a p-phenylene group; R^2 to R^6 are each independently H or a C_1_-_4 alkyl group; n is an integer of 1 to 10; A^1 is NO_2, CN or COOY (wherein Y is H or C_1_-_4 alkyl group);
and A^2 is H or a group defined in A^1] and salts thereof.
and formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) [In the formula, A^3 is the group defined for A^1 in formula (I); m is an integer from 1 to 4; D^2 is the formula (
I) is the group defined for D^1; Ph is p-
is a phenylene group; R^7 to R^1^1 are each independently H or C_1_-_4 alkyl group; p
is an integer from 1 to 10; A^4 is A^ in formula (I)
is an atom or group as defined for 2; and R^1^
2 is the group defined for R^1 in formula (I)]
Alternating single layers of "second NLO compounds" selected from compounds and their salts, provided that in these single layers these two compounds are arranged to have electron vectors in the same direction 1. An optical element with nonlinear optical properties comprising a light-transmissive or reflective support having at least a partial surface coating comprising: 2,1-(4-N-methyl-N-dodecylaminophenyl)-3,8-dimethyl-10-carboxyl-10-
Cyanodeca-1,3,5,7,9-pentaene (“Compound I”) and 1-(4-N-methyl-N-2-carboxyethylaminophenyl)-3,8-dimethyl-10
-cyano-10-dodecyloxycarbonyl-deca-1
, 3,5,7,9-pentaene (“Compound II”), each of these compounds independently in the form of the free acid or their cadmium or calcium salts or methyl a light-transmitting surface having an ester, and substantially all molecules of compounds I and II shall be oriented in the coating with electron vectors parallel and in the same direction; The optical element according to claim 1, comprising a reflective support. 3. The optical element according to claim 2, which has a light-transmitting support and the coating layer is a monomolecular layer. 4. The optical element according to claim 2, which has a light reflective support and the coating layer is thicker than a monomolecular layer. 5. Passing the surface of the optically transparent or reflective support into the liquid subphase through a first surface of the liquid supporting a surface monolayer of a first NLO compound and a surface layer of a second NLO compound. 2. The method of manufacturing an optical element according to claim 1, further comprising removing the liquid from the liquid through the second surface of the liquid supporting the liquid or vice versa. 6. Process according to claim 5, wherein the liquid subphase is an aqueous medium in a Langmuir trough and the monolayer is obtained by adjusting the surface area with a movable dam. 7. An optical device comprising the nonlinear optical element according to claim 1. 8. Claim 7, wherein the optical element is the optical element according to claim 2.
Optical device as described. 9. A compound of formula (II) as defined in claim 1. 10,1-(4-N-methyl-N-2-carboxyethylaminophenyl)-3,8-dimethyl-10-dodecyloxycarbonyl-10-cyanodeca-1,3,5,
10. The compound according to claim 9, which is 7,9-pentaene or a calcium or cadmium salt thereof.