JPH11160745A - Polyselenophene as material having nonlinear optical property and composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an optically stable selenophene compd. which may be produced and processed to a thin film form by a simple process, has an excellent nonlinear characteristic and has a rapid relaxation time and optically high quality by using a nonlinear optical material contg. specific polyselenophene. SOLUTION: This nonlinear optical material contains the polyselenophene having the structural units of formula I or formula II or >=1 kind of the formula I or the formula II. In the forms, X and Y may be same or different and respectively independently denote hydrogen (in this case only either of X and Y is hydrogen), straight or branched 1-22C alkyl group, straight or branched 1-22C alkoxy group, etc. Or X and Y and the atom to which these are bonded may cojointly form a carbon-contg. ring having nitrogen (N), oxygen (O), sulfur (S) or phosphorus (P) hetero atom in addition to a carbon atom or >=2 kinds of these hetero atoms.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel nonlinear optical material containing polyselenophene and a composition containing the same.

[0002]

BACKGROUND OF THE INVENTION It has been disclosed that conjugated organic materials can exhibit non-linear optical effects. This is because the delocalized π electrons in these systems are in a state where they can be easily polarized. Furthermore, the number of double bonds has a significant effect on the nonlinear optical performance of conjugated polyenes.

[0003] Nonlinear optics is completely or totally related to the interaction between the electromagnetic field and the material, and can result in a refractive index that depends on the intensity of the light. RN Prasad and
In this regard, DJ Williams wrote the book "Introduction
to non-linear optical effects in molecules and po
lymers "(Wiley 1991) for more information.

A substance having a tertiary electric polarizability χ ⁽³⁾ has an intensity-dependent refractive index. χ ⁽³⁾ is a material constant that depends on the molecular structure, crystal structure, light frequency, and temperature. It is known that this can be measured by an attenuated four-wave mixing (DFWM) method or a third harmonic generation (THG) experiment.
These methods are described in Prasad and Willia in the above references.
Mainly described in the discussion by ms.

[0005] ⁽³⁾ High value materials are used in optical communication or optical function computers, because they are particularly suitable for the production of pure optical switches. Other possible uses of these materials include:
DR Ulrich, Molecular Crystals Liquid Crystals
160 (1988) 1-31.

In order to use a nonlinear optical material (here, a material having a high χ ⁽³⁾ value ^{) in an} optical component, it is necessary to combine characteristics of various substances. Therefore, the high χ ⁽³⁾ value itself does not satisfy the requirement for the optical component. In addition, relaxation times and switching times should be reduced (in the picosecond or femtosecond range), and optical losses due to absorption and scattering, etc. should be minimized. In particular, this non-linear material must be able to be processed in layers, for example for optical waveguides and the like.

[0007] Usually this material is applied by various thin-layer manufacturing techniques for various materials in the electrical industry. A relatively simple method for producing layers for optical materials is spin coating. This method results in a uniform, transparent layer of either a pure material with non-linear optical activity or a mixture of a transparent matrix polymer and an NLO material. If this method is carried out industrially, it is necessary to apply a homogeneous solution of these substances alone or in combination with a polymer. The thickness of the layer obtained by spin-coating depends on the rheological properties of the solution and the speed of rotation of the material during application.

Films with a layer thickness of> 1 μm are also produced by knife coating and casting techniques.
In order to prevent cracks and non-uniformity from occurring, it is necessary to dry carefully and surely after the application.

It is known that polythiophenes can be made thin (in particular, "Introduction to nonlinear optics").
al effects in molecules and polymers ", P. Prasad
, DJ Williams, Wiley, 1991, "Thire-o
rder optical nonlinearity in polycondensed thiophen
e-based polymers and polysilane polymers '', L. Yang
, R. dorsinville, QZ Wang, WK Zou, PP H
o, NL Yang, RR Alfano, R. Zamboni, R. Danieli
Author, J. Opt. Soc. Am. B .: Opt. Phys., 6 (4) (1989) 7.
53-756, `` Nonlinear-optical response in polythiop
hene films using four-wave mixing techniques ",
R. Dorsinville, L. Yang, RRalfano, R. Zambon
i, R. Danieli, G. Ruani, C. Taliani, Opt. Lett.
, 14 (1989) 1321-1323, `` Frequency variation of cu
bic susceptibility in the new conjugated polymers
(polythieno (3,2-b) thiophene) and poly [1,4-di (2-thi
enyl) benzene], F. Kajzar, G. Ruani, C. Taliani,
R. Zamboni, Synth.Met. 37 (1990) 223-229, `` Conju
gated poly (thiophenes): synthesis, functionalzation
and applications, "J. Roncali, Chem. Rev., 92 (19
92), 711-738, Photoexcitations and nonlinear opti
cal properties in thiopnene based conjuction syste
m, C. Taliani, AJ Pal, G. Rauni, R. Zamboni,
RR Alfano, R. Dorsinville, L. Yang, Proc. SPIE
-Int. Soc. Opt. Eng., 1599 (Recent Adv. Uses Light
Phys., Chem. Eng., Med.) (1992) 24-33).

However, these layers are about 800 nm-1600n, which are technically important for telecommunications and the like.
It has the disadvantage of not having high nonlinearity in the wavelength range of m. Reported on polythiophene by L. Yang et al. ⁽³⁾ Value ("Third-order optical nonlinea
rity in polycondensed thiophene-based polymers and
polysilane polymers ", J. Opt. Soc. Am. B .: Opt.
Phys. 6 (4) (1989) 753-756) has a switching time <
At 12 ps, 3 × 10 ^-11 esu (DFWM, 1064
nm).

The use of specially novel polythiophenes as non-linear optical materials is described in DE 1970985.7. Further details regarding particularly preferred polythiophenes and their preparation can be found in PCT / EP97 /
01140 and the references cited therein.

[0012] The use of polyselenophene as a nonlinear optical material has not been previously disclosed.

[0013]

SUMMARY OF THE INVENTION However, the present invention provides an optically high-quality, light-stable selenophene which can be manufactured and processed into a thin film by a simple method, has excellent non-linear characteristics, has a quick relaxation time, Its purpose is to produce compounds or compositions thereof.

[0014]

The object of the present invention is to provide a compound of the formula (I) or (II) or a compound of the formulas (I) and (I)
I)

[0015]

Embedded image Wherein X and Y may be the same or different, and each independently represents hydrogen (in this case, only one of X and Y is hydrogen), linear or branched C ₁ -C ₂₂ alkyl group, linear or branched C _1-
A C ₂₂ alkoxy group, a linear or branched C ₁ -C ₂₂ alkyloxyalkyl group, a linear or branched C ₁ -C ₂₂
Acyl group, linear or branched C ₁ -C ₂₂ thioacyl group, linear or branched C ₁ -C ₂₂ acyloxy group, linear or branched C ₁ -C ₂₂ thioacyloxy group, C ₅
-C ₈ cycloalkyl group, C ₆ -C ₁₈ aryl group or C ₅ -C ₈ heterocyclic (heterocyclyl) group (each of which is one or more linear or branched C ₁ -C ₂₂ alkyl group, Linear or branched C ₁ -C ₂₂ alkoxy group, one or more linear or branched C ₁ -C ₂₂ alkyloxyalkyl group, one or more linear or branched C ₁ -C ₂₂
May be substituted by ₁ -C ₂₂ acyl group or one or more straight or branched C ₁ -C ₂₂ thioacyl group,),
NO ₂ , or NHR ¹ , wherein R ¹ may be the same or different and each represents hydrogen, linear or branched C
₁ -C ₂₂ alkyl group, linear or branched C ₁ -C ₂₂ alkoxy group, a linear or branched C ₁ -C ₂₂ alkyloxy group, linear or branched C ₁ -C ₂₂ acyl group Or a linear or branched C ₁ -C ₂₂ thioacyl group), or X, Y and the atom to which they are bonded together are nitrogen, nitrogen (N), oxygen (O), sulfur (S) or phosphorus (P) heteroatoms, or a carbon-containing ring having two or more of these heteroatoms may be formed, wherein the ring further comprises a carbon atom, a nitrogen atom or a phosphorus atom. May be substituted by a group represented by Z, wherein Z independently represents a group defined for X and Y above, or two adjacent Zs together represent a group represented by the following formula (III) )-(VI)

[0016]

Embedded image Wherein A represents carbon (C), nitrogen (N), phosphorus (P) or two or more of these atoms, and when A represents carbon, these A are hydrogen It has been found by the inventors that the problem is solved by a nonlinear optical material comprising one or more polyselenophenes, which may be substituted by an atom or a group as defined for X and Y above.

[0017]

In the embodiment of the present invention, the polyselenophene used in the present invention has the formula (XII) or (XIII), or (XII) and (XII).
I)

[0018]

Embedded image Wherein one or more thiophene structural units are present, wherein X and Y may be the same or different, and each independently has the same meaning as defined above for polyselenophene units.

Regarding the method for producing the thiophene unit and the properties of the compound containing this unit in a preferred embodiment, PCT / EP97 / 0114 described at the beginning.
0, and these descriptions in the same document are all applied to the present invention.

"Polyselenophene" used in the present invention
The term is meant to include all polymers or oligomers having one or more units of formula (I) and / or (II). That is, one or more identical units (I) and / or (II) may be present, or a plurality of different units (II) may be present, that is, all units are present in the polyselenophene of the present invention. It may be present one or more times.
The polyselenophene of the present invention has the formula (I) and (II)
It is preferred to have one or more types of units. Further, the present invention includes all polymers and oligomers containing one or more units of formula (I) and / or (II) and one or more thiophene units of formula (XII) and / or (XIII) Is included.

Further, a combination of the units of the formulas (I) and / or (II) with other conjugated organic structural units such as phenylene, biphenylene, terphenylene, naphthalene, anthracene, and furan may be used. Frequently, the conjugated organic structural unit may be mono- or poly-substituted as defined above for X and Y.

The structural unit (I) present in the polyselenophene of the present invention is obtained from selenophene.

In the structural unit (II), X and Y
And when the atoms to which they are attached do not form a carbon-containing ring, X and Y may be the groups described at the beginning, and it is preferred that X and Y are the same. X
And Y are each NHR ¹ , two R
Preferably, ^one group is the same. As described above, 1 carbon atom
-22 alkyl, alkoxy, alkyloxyalkyl, acyl and thioacyl groups having 1 to 20 carbon atoms
Are preferable, those having 6 to 20 carbon atoms are more preferable, and those having 10 to 16 carbon atoms are particularly preferable.

Highly preferred substituents X and Y are acyl, thioacyl and NHR ^{1 as} defined above.

In the present invention, the term "thioacyl group" means a group represented by the formula -C (S) -R (R means alkyl). The term "heterocyclic group" means an alicyclic saturated, alicyclic unsaturated and aromatic heterocyclic group.

In addition, X and Y and the atoms to which they are bonded are cooperated to form a hetero atom of nitrogen (N), oxygen (O), sulfur (S) or phosphorus (P) in addition to carbon, or a hetero atom thereof. A carbon-containing ring having two or more of the atoms may be formed. In this case, X and Y form a divalent group having 2 to 8, more preferably 3 to 6 atoms, and together with the two atoms to which they are bonded, 4 to 10 or 5 to 8
It is preferred to form a ring having three atoms. The number of the above hetero atoms which may be present in this ring is preferably 3 or less, more preferably 2 or less. Of the above heteroatoms, nitrogen (N) is preferred. Preferably said ring has one or more, more preferably two or more, double bonds. In a particularly preferred embodiment of the invention, the double bond in the ring is the double bond of the selenophene moiety to which the ring is attached, and optionally also the formula (III) to (VI) is conjugated to another group.

The ring may be further substituted on the carbon, nitrogen or phosphorus atom by one Z group each Z being independently of one another the groups defined for X and Y above; Further, also in this case, the substituents described as being preferably used for X and Y are preferably used.

Also, two adjacent Z groups may jointly form a group selected from the groups according to the formulas (III) to (VI) mentioned at the outset, in which case the spacer "A" Carbon (C), nitrogen (N), phosphorus (P) or a combination of two or more of these atoms. When A is carbon, it has a hydrogen atom or has the same meaning as defined for X and Y above. May be further substituted. In this case, it is preferred that these groups form another ring together with the atoms to which they are bonded, and form a conjugated unsaturated system together with the other rings in the structural unit.

A preferred ring thus obtained is a cyclobutene ring.

Preferred examples of the polyselenophene used according to the invention include compounds of the formula (VII) and / or (VI
Those having the structural unit represented by II) are included.

[0031]

Embedded image In the above formula, X and Y are the same as defined above, and n, m and k are each independently an integer of 1 to 10, preferably 1 to
6 is an integer, and 1 represents an integer of 1 to 3000, preferably an integer of 1 to 1000, particularly an integer of 1 to 100. In this case, it is preferred that the substituted selenophene units and the unsubstituted selenophene units are alternately continuous.

The structural unit (II) of polyselenophene particularly preferably used is represented by the following formula (II)
Any of the groups represented by a) to (IIg) is used.

[0033]

Embedded image

[0034]

Embedded image The formula R _² = CH ² R ¹ or _{^{R 2 = CHR 1 2, R}} 1
= H or as defined above.

Among the above structural units (II), the following structural units are particularly preferred. In this case, it is obvious that they are derived from the corresponding corresponding compounds which are disubstituted near the selenium atom of selenophene.

Examples of individual structural units are as follows.

3,4-di (decyl) selenophene, 3,
4-di (undecyl) selenophene, 3,4-di (dodecyl) selenophene, 3,4-di (tridecyl) selenophene, 3,4-di (tetradecyl) selenophene,
3,4-di (pentadecyl) selenophene, 3,4-di (hexadecyl) selenophene, 3,4-di (heptadecyl) selenophene and 3,4-di (octadecyl)
Selenophene structural unit, 3,4-di (2-decyloxy) selenophene, 3,4-di (undecyloxy) selenophene, 3,4-di (dodecyloxy) selenophene, 3,4-di (tridecyloxy) selenophene ,
3,4-di (tetradecyloxy) selenophene, 3,
4-di (pentadecyloxy) selenophene, 3,4-
Di (hexadecyloxy) selenophene, 3,4-di (heptadecyloxy) selenophene and 3,4-di (octadecyloxy) selenophene structural units, more preferably the above ether groups are substituted with the corresponding thioether groups Structural unit, 3,4-di (decyloxyethyl) selenophene, 3,4-di (undecyloxyethyl) selenophene, 3,4-di (dodecyloxyethyl) selenophene, 3,4-di (tridecyloxyethyl) ) Selenophene, 3,4-di (tetradecyloxyethyl) selenophene, 3,4-di (pentadecyloxyethyl) selenophene, 3,4-di (hexadecyloxyethyl) selenophene, 3,4-di (heptadecyl) Oxyethyl) selenophene and 3,4-di (octadecyloxyethyl) sele Fen structural units, more preferably an oxygen atom alkyloxyalkyl group as defined above, depending on the length of the entire substituents, 3, 3,6,
Structural units at positions 3,6,9-, 3,6,9,12-, such as 3,4-di (2-ethyldecyloxy) selenophene, 3,4-di (3-propyloxydecyl)
Selenophene, 3,4-di (4-butyloxydecyl)
3,4-di (2- (2- (decyloxy) ethoxy) ethyl) selenophene, 3,4-di (2
-(2- (undecyloxy) ethoxy) ethyl) selenophene, 3,4-di (2- (2- (dodecyloxy)
Ethoxy) ethyl) selenophene or the like having a total number of carbon atoms not exceeding 22, more preferably an alkyloxyalkyl-substituted oxygen atom-substituted structural unit as defined above, 3,4-di (cyclopentyl) selenophene, 3,4-di (cyclopentenyl) selenophene,
3,4-di (cyclohexyl) selenophene, 3,4-
Di (cyclohexenyl) selenophene, 3,4-di (cyclohexadienyl) selenophene, 3,4-di (phenyl) selenophene and 3,4-di (benzyl) selenophene structural units (the substituents are as defined for R ¹ ) 1
3,4-di (decanoyl) selenophene, 3,4-di (undecanoyl) selenophene, 3,4-di (dodecanoyl) selenophene, 3,4-di (tridecanoyl) Selenophene, 3,
4-di (tetradecanoyl) selenophene, 3,4-di (pentadecanoyl) selenophene, 3,4-di (hexadecanoyl) selenophene, 3,4-di (heptadecanoyl) selenophene and 3,4-di ( Octadecanoyl) selenophene structural units and corresponding alkanoyloxy structural units such as 3,4-di (decanoyloxy) selenophene, 3,4-di (undecanoyloxy) selenophene, and more preferably a carbonyl group thereof. A group substituted with a thiocarbonyl group, 3,4-di (decanoylamino) selenophene, 3,4-di (undecanoylamino) selenophene, 3,4-di (dodecanoylamino) selenophene, Di (tridecanoylamino) selenophene, 3,4-di (tetradecanoylamino) selenophene 3,4-di (pentadecanoylamino) selenophene, 3,4-di (hexadecanoylamino) selenophene, 3,4-di (heptadecanoylamino) selenophene and 3,4-di (octadecanoylamino) The structural unit of selenophene, also in this case 2,3-dipentylseleno [3,4-b] pyrazine, 2,3-didecylseleno [3,4-b] pyrazine, in which the oxygen atom may be replaced by sulfur, 2 , 3-Diundecylseleno [3,4-b] pyrazine, 2,3-didodecylseleno [3,4-b] pyrazine, 2,3-ditridecylseleno [3,4-b] pyrazine, 2,3 -Ditetradecylseleno [3,4-b] pyrazine, 2,3-dipentadecylseleno [3,4-b] pyrazine, 2,3-dihexadecylseleno [3,4-b] pyrazine, 2, 3 Di heptadecyl seleno [3,4-b] pyrazine and 2,3-dioctadecyl seleno [3,4-b] pyrazine structural units, 2-
Methyl-3-decyloxyseleno [3,4-b] pyrazine, 2-methyl-3-undecyloxyseleno [3,4
-B] pyrazine, 2-methyl-3-dodecyloxyseleno [3,4-b] pyrazine, 2-methyl-3-tridecyloxyseleno [3,4-b] pyrazine, 2-methyl-
3-tetradecyloxyseleno [3,4-b] pyrazine, 2-methyl-3-pentadecyloxyseleno [3
4-b] pyrazine, 2-methyl-3-hexadecyloxyseleno [3,4-b] pyrazine, 2-methyl-3-octadecyloxyseleno [3,4-b] pyrazine, 2-
Methyl-3-eicosyloxyseleno [3,4-b] pyrazine, 2-methyl-3-docosyloxyseleno [3,
4-b] pyrazine, 2-ethyl-3-decyloxyseleno [3,4-b] pyrazine, 2-ethyl-3-undecyloxyseleno [3,4-b] pyrazine, 2-ethyl-
3-dodecyloxyseleno [3,4-b] pyrazine, 2
-Ethyl-3-tridecyloxyseleno [3,4-b]
Pyrazine, 2-ethyl-3-tetradecyloxyseleno [3,4-b] pyrazine, 2-ethyl-3-pentadecyloxyseleno [3,4-b] pyrazine, 2-ethyl-
3-hexadecyloxyseleno [3,4-b] pyrazine, 2-ethyl-3-octadecyloxyseleno [3
4-b] pyrazine, 2-ethyl-3-eicosyloxyseleno [3,4-b] pyrazine, 2-ethyl-3-docosyloxyseleno [3,4-b] pyrazine structural unit, 2
-Phenyl-3-decyloxyseleno [3,4-b] pyrazine, 2-phenyl-3-undecyloxyseleno [3,4-b] pyrazine, 2-phenyl-3-dodecyloxyseleno [3,4- b] pyrazine, 2-phenyl-
3-tridecyloxyseleno [3,4-b] pyrazine,
2-phenyl-3-tetradecyloxyseleno [3,4
-B] pyrazine, 2-phenyl-3-pentadecyloxyseleno [3,4-b] pyrazine, 2-phenyl-3-
Hexadecyloxyseleno [3,4-b] pyrazine, 2
-Phenyl-3-heptadecyloxyseleno [3,4-
b] pyrazine, 2-phenyl-3-octadecyloxyseleno [3,4-b] pyrazine, 2-phenyl-3-eicosyloxyseleno [3,4-b] pyrazine- and 2-phenyl-3-docosyl Oxyseleno [3,4-
b] pyrazine structural unit (again, an oxygen atom may be replaced by sulfur), 2,3-di (decyloxy) seleno [3,4-b] pyrazine, 2,3-di (undecyloxy) Seleno [3,4-b] pyrazine, 2,3-di (dodecyloxy) seleno [3,4-b] pyrazine, 2,3
-Di (tridecyloxy) seleno [3,4-b] pyrazine, 2,3-di (tetradecyloxy) seleno [3,4
-B] pyrazine, 2,3-di (pentadecyloxy) seleno [3,4-b] pyrazine, 2,3-di (hexadecyloxy) seleno [3,4-b] pyrazine, 2,3-di (Heptadecyloxy) seleno [3,4-b] pyrazine and 2,3-di (octadecyloxy) seleno [3
4-b] pyrazine, 2,3-di (eicosyloxy) seleno [3,4-b] pyrazine and 2,3-di (docosyloxy) seleno [3,4-b] pyrazine structural units, more preferably still A structural unit in which an ether group according to the above definition is substituted with a corresponding thioether group, 2,3-di (decyloxyethyl) seleno [3,4-b] pyrazine,
2,3-di (undecyloxyethyl) seleno [3,4
-B] pyrazine, 2,3-di (dodecyloxyethyl)
Seleno [3,4-b] pyrazine, 2,3-di (tridecyloxyethyl) seleno [3,4-b] pyrazine, 2,
3-di (tetradecyloxyethyl) seleno [3,4-
b] pyrazine, 2,3-di (pentadecyloxyethyl) seleno [3,4-b] pyrazine, 2,3-di (hexadecyloxyethyl) seleno [3,4-b] pyrazine, 2,3- Di (heptadecyloxyethyl) seleno [3,4-b] pyrazine and 2,3-di (octadecyloxyethyl) seleno [3,4-b] pyrazine structural units, more preferably oxygen of an alkoxyalkyl group as defined above Atoms are 3-, depending on the total length of the substituents,
Structural units at positions 3,6-, 3,6,9-, 3,6,9,12- and the like, for example, 2,3-di (2-ethyloxydecyl) seleno [3,4-b] pyrazine 2,3-di (3-propyloxydecyl) seleno [3,4-b] pyrazine and 2,3-di (4-butyloxydecyl) seleno [3,4-b] pyrazine; Di (2- (2-decyloxy) ethoxy) ethyl) seleno [3,4-b]
Pyrazine, 2,3-di (2- (2- (undecyloxy) ethoxy) ethyl) seleno [3,4-b] pyrazine, 2,3-di (2- (2- (dodecyloxy) ethoxy) ethyl ) Seleno [3,4-b] pyrazine and the like, in which case the total number of carbon atoms does not exceed 22;
More preferably, a structural unit wherein the oxygen atom of the alkyloxyalkyl substituent as defined above is replaced by sulfur;
-Di (cyclopentyl) seleno [3,4-b] pyrazine, 2,3-di (cyclopentenyl) seleno [3,4-
b] pyrazine, 2,3-di (cyclohexyl) seleno [3,4-b] pyrazine, 2,3-di (cyclohexenyl) seleno [3,4-b] pyrazine, 2,3-di (cyclohexadienyl) ) Seleno [3,4-b] pyrazine;
2,3-di (phenyl) 1 according seleno [3,4-b] pyrazine and 2,3-di (benzyl) seleno [3,4-b] pyrazine structural units (the substituent is further defined for R ¹
5,6-di (decyloxy) cyclobuta [b] seleno [3,4-e] pyrazine, 5,6-di (undecyloxy) cyclobuta [b]
Seleno [3,4-e] pyrazine, 5,6-di (dodecyloxy) cyclobuta [b] seleno [3,4-e] pyrazine, 5,6-di (tridecyloxy) cyclobuta [b]
Seleno [3,4-e] pyrazine, 5,6-di (tetradecyloxy) cyclobuta [b] seleno [3,4-e] pyrazine, 5,6-di (pentadecyloxy) cyclobuta [b] seleno [ 3,4-e] pyrazine, 5,6-di (hexadecyloxy) cyclobuta [b] seleno [3,4-
e] pyrazine, 5,6-di (heptadecyloxy) cyclobuta [b] seleno [3,4-e] pyrazine and 5,
6-di (octadecyloxy) cyclobuta [b] seleno [3,4-e] pyrazine structural unit, more preferably a structural unit in which an ether group as defined above is substituted by a corresponding thioether group, 5,6-di (cyclopentyloxy) ) Cyclobuta [b] seleno [3,4-e] pyrazine, 5,6
-Di (cyclopentenyloxy) cyclobuta [b] seleno [3,4-e] pyrazine, 5,6-di (cyclohexyloxy) cyclobuta [b] seleno [3,4-e] pyrazine, 5,6-di ( Cyclohexenyloxy) cyclobuta [b] seleno [3,4-e] pyrazine, 5,6-di (cyclohexadienyloxy) cyclobuta [b] seleno [3,4-e] pyrazine, 5,6-di (phenyl) ) Cyclobuta [b] seleno [3,4-e] pyrazine and 5,6-di (benzyl) cyclobuta [b] seleno [3
4-e] pyrazine structural unit (the above substituents may be substituted with one or more groups as defined for R ¹ ), 2-decyl-1H-seleno [3,4-d] imidazole, 2-
Undecyl-1H-seleno [3,4-d] imidazole, 2-dodecyl-1H-seleno [3,4-d] imidazole, 2-tridecyl-1H-seleno [3,4-d]
Imidazole, 2-tetradecyl-1H-seleno [3,
4-d] imidazole, 2-pentadecyl-1H-seleno [3,4-d] imidazole, 2-hexadecyl-1
Structural unit of H-seleno [3,4-d] imidazole, 2-heptadecyl-1H-seleno [3,4-d] imidazole and 2-octadecyl-1H-seleno [3,4-d] imidazole, 2-cyclopentyl -1H-seleno [3,4-d] imidazole, 2-cyclopentenyl-
1H-seleno [3,4-d] imidazole, 2-cyclohexyl-1H-seleno [3,4-d] imidazole,
2-cyclohexenyl-1H-seleno [3,4-d] imidazole, 2-cyclohexadienyl-1H-seleno [3,4-d] imidazole, 2-phenyl-1H-seleno [3,4-d] imidazole And 2-benzyl-
1H-seleno [3,4-d] imidazole structural unit, 2
-Butylthio-1H-seleno [3,4-d] imidazole, 2-pentylthio-1H-seleno [3,4-d] imidazole, 2-hexylthio-1H-seleno [3,4
-D] imidazole, 2-heptylthio-1H-seleno [3,4-d] imidazole, 2-octylthio-1H
-Seleno [3,4-d] imidazole-, 2-nonylthio-1H-seleno [3,4-d] imidazole, 2-decylthio-1H-seleno [3,4-d] imidazole,
2-undecylthio-1H-seleno [3,4-d] imidazole, 2-dodecylthio-1H-seleno [3,4-
d] Imidazole, 2-tridecylthio-1H-seleno [3,4-d] imidazole, 2-tetradecylthio-
1H-seleno [3,4-d] imidazole, 2-pentadecylthio-1H-seleno [3,4-d] imidazole, 2-hexadecylthio-1H-seleno [3,4-
d] imidazole, 2-heptadecylthio-1H-seleno [3,4-d] imidazole, 2-octadecylthio-1H-seleno [3,4-d] imidazole structural units (these substituents being further defined by R ¹⁾ May be substituted with one or more groups).

The proportion of the structural units (I) and (II) as defined above in the polyselenophene of the present invention is from about 1 to about 99 mol% of (I) and from about 99 to about 1 mol% of (II),
Preferably about 30 to about 70 mole% of (I) and about 70 mole%
To about 30 mol% of (II), particularly preferably about 50 mol% of (I) and about 50 mol% of (II). In each case, the proportion of these two structural units is a total. At 100
Mol%. It is preferable that the two structural units (I) and (II) are alternately repeated.

The weight average molecular weight (M _w ) of the polyselenophene used according to the present invention, as determined by gel permeation chromatography using polystyrene as a standard, generally ranges from about 1000 to about 50,000.
0, preferably in the range of about 10,000 to about 250,000, especially in the range of about 30,000 to about 80,000.
The degree of non-uniformity of the molecular weight distribution, that is, the quotient ( _Mw / _Mn ) of the weight average molecular weight and the number average molecular weight is about 2 to about 4, preferably about 2 to about 3, especially about 2 to about 2.5. It is.

The polyselenophenes of the invention can be polymerized by any reaction suitable for pyrrole or thiophene, for example by the chemical or electrochemical oxidation mentioned at the outset. Polyselenophene having alkyl, alkoxy, acylamino or alkoxyalkyl substituents and the like can also be reacted by catalytic coupling of an organometallic compound (usually a Grignard reagent). For details of this reaction, see PCT / EP97 / 011 at the beginning.
40 and the references mentioned therein.

However, preferred methods for producing the polyselenophene of the present invention are the Stille reaction and the Suzuki reaction (A. Suzuki et al., "Stereoselec").
tive synthesis of arylated (E) -alkenes by the reac
tion of alk-1-enylboranes with aryl halides in the
presense of palladium catalyst ", JCS Chem. Co
mm., 1979, pp. 866-867), which is described in detail below.

In the Suzuki reaction, a 2,5-dihalo- or 2,5-triflate-substituted selenophene corresponding to the structural unit (II) of the present invention is converted to selenophene diborate or selenophene diborate with a base, preferably The reaction is carried out in the presence of sodium methoxide and a palladium complex having a structure of PdL ₄ (L = ligand, preferably Pd (PPh ₃ ) ₄ ).

[0043]

Embedded image Sub = halogen or triflate X, Y = same as defined above R = H or alkyl

The preferred borane used in this reaction is
Selenophene-2,5-diboric acid and its esters. Further details of this reaction are described in the references cited above.

In carrying out the Suzuki reaction, the above structural units
The diboric acid (ester) derivative of the selenophene derivative corresponding to (II) is reacted with a 2,5-dihalo- or 2,5-triflate-substituted selenophene corresponding to the structural unit (I).

However, a particularly preferred method for producing the polyselenophenes according to the invention is the still reaction already mentioned at the outset. In this reaction, 2,5-dihaloselenophene or 2,5-ditriflate selenophene is substituted with bis (trialkyltin) on the carbon atom adjacent to selenium corresponding to the structural unit (II) as defined above. Or a 2,5-bis (trialkyltin) selenophene and a bis (halogen) -substituted or bis (triflate) atom on a carbon atom adjacent to selenium corresponding to the structural unit (II) defined above. ) The substituted thiophene derivative is reacted with a suitable P as a catalyst in a suitable solvent.
In the presence of d (0) or Pd (II) complex or a salt thereof, they are reacted with each other according to the following formula.

[0047]

Embedded image Sub = halogen or triflate k ′ = 1, 2, 3,..., 10

As the substituent "Sub" in the above formula, a halogen-substituted derivative is preferably used. If bis (triflate), ie (CF ₃ SO ₃ ) -substituted precursors are used, for example, LiCl can be added to improve the reactivity.

Due to the mild reaction conditions for carrying out this reaction, all kinds of substituents, such as, for example, amine, acyl, ester, ether and nitro groups, are tolerated.

The catalyst used is Pd (II) or Pd
(0) complex. Preferred catalysts include tris (dibenzylideneacetone) dipalladium (Pd ₂ db).
a ₃ ), Pd (Ph ₃ P) ₂ Cl ₂ (where Ph is C ₆
Means H _5), and Pd (Ph ₃ P) ₄ can be mentioned. In the case of using tris (dibenzylideneacetone) dipalladium, various ligands can be used, and the ligand exchange between the weakly coordinated Pd ₂ dba ₃ and the ligand enables the catalytic activity in situ. A catalyst PdL ₄ having the formula: The ligand used in this case is P
Ph ₃ , AsPH ₃ , [2- (CH ₃ ) C ₆ H ₄ ] ₃
P, P (OPh) ₃ and (2-furyl) ₃ P and the like. The amount of catalyst used is about 2 to about 10 mole%, preferably about 2 to about 5 mole%, based on the bis (trialkyltin) substituted precursor used.

In general, any solvent that can maintain the precursor and catalyst in solution can be used, but DM
F, NMP and cyclic ethers, such as THF and dioxane, are the most preferred solvents. Of these, DMF and THF are preferred.

Generally, the reaction is carried out at a temperature between room temperature and the boiling point of the solvent, with a temperature of about 50 ° C to about 100 ° C being preferred. Depending on the starting materials and / or catalysts used,
The reaction time is one day to one month, preferably one day to one week.

A similar method is used to prepare copolymers or cooligomers having thiophene and / or other conjugated organic units.

By this relatively mild reaction, it is possible to produce polyselenophene having the following excellent properties. The resulting selenophene shows little or no structural defects, aging (doping) or peroxidation; acceptors, donors and multiple molecules between carbon and heteroatoms It is possible to introduce a large number of functional groups including a π system including a bond, etc.Moreover, it is possible to produce a strictly alternating copolymer selenophene having plural kinds of rings substituted in various forms. .
Specifically, performing a reaction between selenophene substituted at the 3- and 4-positions and unsubstituted thiophene (it is extremely difficult according to the methods generally used so far for producing polyselenophene). Is) possible.

The Suzuki reaction also has the above advantages as compared with the conventional method. However, in the present invention, the still reaction is particularly preferably used because the still reaction does not require an additional base unlike the Suzuki reaction. You.

That is, the present invention further relates to 2,5-dihaloselenophene or 2,5-ditriflate selenophene, which corresponds to the above structural unit (II) and has a bis (trialkyl group) on the carbon adjacent to selenium. Tin) substituted one or more selenophene derivatives with a suitable P
one or more polyselenophenes obtained by reacting in the presence of a d (0) or Pd (II) complex,
3 discloses use in a nonlinear optical material in the present invention. Further, the present invention relates to 2,5-bis (trialkyltin) selenophene and one of bis (halo) -substituted or bis (triflate) -substituted carbon atoms adjacent to selenium corresponding to the above structural unit (II) The above selenophene derivative is combined with Pd as a catalyst in a suitable solvent.
It discloses the use of one or more selenophenes obtained by reacting in the presence of a (0) or Pd (II) complex in the above nonlinear optical material.

The present invention further relates to the following component (a)
And (b), that is, a composition having nonlinear optical properties, comprising (a) one or more of the above-mentioned polyselenophenes and (b) one or more other polymers.

The component (b) in this composition is an amorphous polymer. Specific examples thereof include polymers based on vinyl acetate, vinylamine, vinylimidazole or vinylpyrrolidone. In addition, polymers based on one or more acrylamides or acrylamides such as alkylacrylamides, preferably methacrylamide, are also suitable. Similarly, it is also possible to use polymers based on one or more acrylimides or alkylacrylimides, preferably methacrylimides, as component (b).

The composition may contain a random copolymer or a block copolymer, or a mixture of different polymers (b). Particularly preferred are polyvinylpyrrolidone and a copolymer based on a monomer selected from N-vinylpyrrolidone, N-vinylimidazole and vinyl acetate.

These polymers are known, and are usually 200
00 to 15000000, preferably 40000 to 120
It has a weight average molecular weight of 0000. Similarly, the preparation of these polymers is known, or these polymers can be prepared by known methods, see the relevant literature in this regard.

The proportion of the polymer component (b) in the composition is usually in the range of 79.9 to 95% by weight. Preferred compositions are 81.8-92% by weight, especially 84.6-90% by weight.
(B). The balance of the composition is the polyselenophene used in the present invention, wherein component (a)
And the sum of (b) is 100%.

The polyselenophene films used according to the invention can be prepared by pouring a carefully filtered or centrifuged solution in chloroform or trichlorethylene onto a glass substrate. According to this method, a uniform film having a thickness of 300 nm or less can be manufactured. The optical quality of this film is high and light scattering is negligible.

The invention further relates to a film or sheet comprising one or more polyselenophene as defined above, or one or more compositions as defined above.

The method for producing polyselenophene used in the present invention and the starting materials used in this production will be further described below with reference to some examples.

[0065]

Example 1 Starting from selenophene 1, via 2,5-dilithium derivative 2, 2,5-bis (trimethyltin) selenophene (A) was obtained directly. Compound 2 is described in the reaction for the corresponding thiophene, BJ Wakefi
eld, "Organolithium methods", Academid Press
1988, pp. 47-48 (Russian) and the literature cited therein by the reaction of BuLi / hexane with TMEDA under reflux. This reaction is described in Reaction Scheme 1 below.

[0066]

Embedded image i: 2.5 equivalents of BuLi / TMEDA, hexane, under reflux ii: (CH ₃ ) ₃ SnCl, hexane, 0 ° C., room temperature

After recrystallization twice from hexane, compound A
An analytically pure sample was obtained. The structure (and purity) of Compound A was confirmed by 1H-NMR spectroscopy.

Compound A had a melting point of 123-124 ° C. (hexane). ¹ H-NMR (200 MHz, CDCl ₃ , δ, pp
m): 0.38 s (CH ₃ ), 0.38 d (CH ₃ , J
(117Sn-1H) = 56.7 Hz), the total intensity of the two signals: 9H), 7.70 s (H ^ar ), by spin-spin coupling ( ³ J) and ¹¹⁷ Sn / ¹¹⁹ Sn and ⁷⁷ Se.
A total intensity corresponding to 1H, symmetric multiplet at about 7.70 ppm was observed.

[0069]

Example 2 Starting from 2-iodoselenophene 3 and 2- (trimethyltin) selenophene 5, 2,2′-
Biselenophene 6 was obtained. 2-Iodoselenophene
Russ. J. of Gernal Chem., 26 (1956) 315, Yurjev et al.
It was obtained by referring to the discussion in 4.

2- (trimethyltin) selenophene 5 is
It is obtained by quenching 2-lithium selenophene with trimethyltin chloride. Starting from selenophene, one equivalent of butyllithium in hexane, T
It was selectively obtained by reaction in the presence of MEDA (N, N, N ', N'-tetramethylethylenediamine).

A still reaction between 2-iodoselenophene and 2- (trimethyltin) selenophene yielded a dimer of 2,2'-biselenophene 6 as a main product. The yield of compound 6 after formation on silica gel and removal of trimer 9 was 69% based on the amount of compound 3 used.

The above reaction is further explained by the following reaction formula 2. The melting point of compound 6 was 36-38 (hexane).

¹ H-NMR (200 MHz, CDCl
₃ , δ, ppm): 7.3 m (2H, ^Hb + ^Hc ),
^{7.94d (1H, H a, J} ab 4.5Hz), 7.94
A doublet (dd) in the low-intensity doublet concentrated in ppm was also observed, ² J ( ⁷⁷ Se-H) = 47 Hz, J _ab =
5.4 Hz, integration intensity of this dd: ⁷⁷ corresponds to the natural content of Se (7.6), 6% of the main signal strength.

[0074]

Embedded image i: I ₂ / HgO, benzene ii: BuLi / TMEDA, hexane, 0 ° C. to room temperature (RT) iii: (CH ₃ ) ₃ SnCl, hexane, 0 ° C. to R
Tiv: 5 mol% Pd (Ph ₃ P) ₂ Cl ₂ , THF,
reflux

As shown in the lower part of Reaction Scheme 3, compound 6
Is also obtained from 2-bromoselenophene 7. This compound is described in Suginome, S. Umezawa, Bull. Chem.
Soc., 11 (No. 3), (1936) 157-167. The yield is about 20% based on the amount of compound 7 used.

[0076]

Embedded image i: Br ₂ / CS ₂ , 0 ° C. to RT ii: Mg, THF, reflux iii: Ni (dppp) Cl ₂ , THF, reflux

[0077]

Example 3 As shown in the following reaction formula 4, starting from 2-iodoselenophene 3 and 2,5-bis (trimethyltin) selenophene A, 2,2 ′: 5 ′, 2 ″- Terselenophene 9 was obtained.

[0078]

Embedded image

Compound 9 was obtained in a yield of 42% and purified on silica gel. The melting point of compound 9 was 169-171 ° C.

¹ H-NMR (200 MHz, CDCl
₃ , δ, ppm): 7.3 m (2H, ^Hb + ^Hc ),
^{7.94d (1H, H a, J} ab 4.5Hz), 7.88
A doublet (dd) in the low-intensity doublet concentrated in ppm was also observed, ² J ( ⁷⁷ Se-H) = 47 Hz, J _ab =
6.3 Hz.

Then, as shown in the following reaction formula 5, compound 9 was converted to compound C, and compound C was obtained in a yield of 24% based on starting compound 9. In order to purify the reaction product obtained, it was washed with cold pentane. Compound C decomposed when heated to about 70 ° C.

¹ H-NMR (200 MHz, CDCl
₃ , δ, ppm): 0.38d (CH ₃ , J ( ¹¹⁷ Sn)
⁻¹ H) = J ¹⁹⁹ Sn− ¹ H) = 56.3 Hz), total strength of two signals: 18H), 7.13 s (2H, Hc),
^{7.32d (2H, H a / H} b, J3.6Hz), 7.
^{37d (2H, H b / H} a, J3.6Hz).

[0083]

Embedded image i: BuLi, TMEDA, THF, -10 ° C. to RT ii: (CH ₃ ) ₃ SnCl, THF

[0084]

EXAMPLE 4 In Reaction Scheme 5, starting from 2,2'-biselenophene 6 as described for trimer C, and as described in Example 3,

[0085]

Embedded image 2,5′-bis (trialkyltin) -5 represented by
2′-Diselenophene (B) was produced.

The melting point of Compound B was 113-115 (hexane).

¹ H-NMR (200 MHz, CDCl
₃ , δ, ppm): 0.38 s (CH ₃ , J ( ¹¹⁷ Sn)
^{- 1 H) = J 199 Sn-} 1 H) = 56.2Hz), total intensity of the two signals: 9H), 7.36m (2H, H ar).

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI // (C08L 65/00 101: 00) (72) Inventor Wolfgang, Schloff Germany, 67271, Neureiningen, Inn, Den, Shell Meneköln, 38

Claims (5)

[Claims] 1. Formula (I) or (II), or Formulas (I) and (II) Wherein X and Y may be the same or different, and each independently represents hydrogen (in this case, only one of X and Y is hydrogen), linear or branched C ₁ -C ₂₂ alkyl group, linear or branched C _1-
A C ₂₂ alkoxy group, a linear or branched C ₁ -C ₂₂ alkyloxyalkyl group, a linear or branched C ₁ -C ₂₂
An acyl group, a linear or branched C ₁ -C ₂₂ thioacyl group, a linear or branched C ₁ -C ₂₂ thioacyloxy group, a linear or branched C ₁ -C ₂₂ acyloxy group,
₅ -C ₈ cycloalkyl group, C ₆ -C ₁₈ aryl group, or a C ₅ -C ₈ Hajime Tamaki (which respectively one or more linear or branched C ₁ -C ₂₂ alkyl group, one or more Linear or branched C ₁ -C ₂₂ alkoxy group, one or more linear or branched C ₁ -C ₂₂ alkyloxyalkyl groups, one or more linear or branched C ₁ -C ₂₂ acyl Group, or optionally substituted by one or more linear or branched C ₁ -C ₂₂ thioacyl groups), NO ₂ , or NHR ¹ , wherein R ¹ may be the same or different;
A hydrogen, a linear or branched C ₁ -C ₂₂ alkyl group, a linear or branched C ₁ -C ₂₂ alkoxy group, a linear or branched C ₁ -C ₂₂ alkyloxyalkyl group, Or a branched or branched C ₁ -C ₂₂ acyl group, a linear or branched C ₁ -C ₂₂ thioacyl group), or X and Y, together with the atom to which they are bonded, In addition to carbon atoms, nitrogen (N), oxygen (O), sulfur (S) or phosphorus (P) heteroatoms, or a carbon-containing ring having two or more of these heteroatoms may be formed. The ring may be substituted on the carbon, nitrogen or phosphorus atom by a group represented by Z, each Z independently representing a group as defined above for X and Y, or two adjacent groups. Z together with the following formula (II)
I)-(VI) Wherein A represents carbon (C), nitrogen (N), phosphorus (P) or two or more of these atoms, and when A represents carbon, these A are hydrogen A nonlinear optical material comprising one or more polyselenophenes, which may be substituted by an atom or a group as defined for X and Y above. 2. The polyselenophene having the following formula (VII) or (VIII): Or having both of them as structural units, wherein X and Y have the same meaning as defined in claim 1, n, m and k each independently represent an integer of 1 to 10, l The nonlinear optical material according to claim 1, wherein is an integer of 1 to 3000. 3. The structural unit (II) is represented by the following formula (IIa):
(IIg) Embedded image A combination of a, or of any group, the group the formula R ¹ is as defined in claim 1, R ² means a CHR ¹ ₂ or CH ₂ R ^1, claim 1 or 3. A nonlinear optical material comprising one or more polyselenophenes according to 2. 4. The following components (a) and (b): (a) one or more polyselenophenes according to any of claims 1 to 3, and (b) one or more other polyselenophenes. And a polymer, wherein the components (a) and (b) have different nonlinear optical properties. 5. A film or sheet having non-linear optical properties, comprising one or more polyselenophenes according to claim 1 or one or more compositions according to claim 4.