JP2005258388A - Organic nonlinear optical material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic nonlinear optical material with high light emission efficiency which has a large two-photon absorption cross-sectional area, which easily induces two-photon absorption, which has large Stokes shift and which efficiently gives fluorescent light generating by the two-photon excitation. <P>SOLUTION: The organic nonlinear optical material contains a compound expressed by general formula (I): (Ar<SP>2</SP>)<SB>m</SB>-Ar<SP>1</SP>-(Ar<SP>3</SP>)<SB>n</SB>as at least part of the structural component. In formula (I), Ar<SP>1</SP>represents a bivalent heterocyclic group expressed by general formula (II), each of Ar<SP>2</SP>and Ar<SP>3</SP>independently represents an aromatic heterocyclic group or an aromatic hydrocarbon cyclic group which may have a substituent, each of m and n represents an integer 1 to 4, and when m and/or n is ≥2, two or more of Ar<SP>2</SP>and/or Ar<SP>3</SP>may be the same or different from each other, or Ar<SP>2</SP>and Ar<SP>1</SP>, or Ar<SP>1</SP>and Ar<SP>3</SP>are coupled with each conjugate connected. In formula (II), ring A and ring Z represent condensed rings having two carbon atoms in common, and each may have a substituent. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an organic material having nonlinear optical characteristics, and more particularly to an organic wavelength conversion material having a large multiphoton absorption cross-section, and more specifically, a large two-photon absorption cross-section and a luminous efficiency from a compound excited by two-photon absorption. It relates to large organic nonlinear optical materials.

Non-linear effects are various phenomena based on the interaction between strong light and matter, and specific phenomena include optical harmonic generation and light mixing, stimulated scattering, light intensity change of optical constants, multiphoton absorption, etc. It is done. In recent years, organic compounds such as 2-methyl-4-nitroaniline as a second-order nonlinear optical material have been reported to exhibit nonlinear optical constants far exceeding those of LiNbO ₃ , LiTaO _{3, and the} like that have been used so far. As a result, organic nonlinear optical materials have attracted attention, and research has been actively conducted.

  Among the nonlinear optical properties possessed by organic compounds, the two-photon absorption phenomenon has attracted particular attention. Two-photon absorption is a phenomenon in which a compound absorbs two photons and transitions from a ground state to an excited state. Using light having a wavelength about twice the one-photon excitation wavelength, two photons are converted into one molecule. It can be excited by applying to. The probability that two photons hit one molecule at a time is proportional to the square of the photon density, and as the laser beam is focused on the sample, the photon density is proportional to the square of the distance as it moves away from the focal plane. Decrease. Accordingly, the probability that two-photon absorption occurs decreases as the distance from the focal plane increases in proportion to the fourth power of the distance. Utilizing this phenomenon, application of two-photon absorption is expected in the fields of optical memory, two-photon modeling, two-photon photodynamic therapy, and the like. In addition, two-photon emission that emits light in a radiation deactivation process from an excited state that has been absorbed by two photons can extract light having a wavelength shorter than the wavelength of the incident light (= light with high energy). As well as research.

  What is important in the application of two-photon absorption in various fields is the two-photon absorption cross section indicating the likelihood of two-photon absorption. In recent years, compounds with a high two-photon absorption cross section have been developed by Chem. Mater. ., 10 (7), 1863 (1998), Tetrahedron Lett., 44, 8121 (2003), Polymer 44, 6851 (2003), Chem. Commun., 2003, 2168. However, these compounds have a small difference (Stokes shift) between the linear maximum absorption wavelength and the fluorescence wavelength (for example, the Stokes shift of the compounds described in Table 1 of Chem. Mater., 10 (7), 1863 (1998) is the maximum). Therefore, there is a drawback that reabsorption of fluorescence generated by two-photon excitation occurs.

On the other hand, it is known that terphenyl and stilbene in which aromatic rings are connected by a conjugated chain have strong fluorescence, and many fluorescent compounds having these skeletons as a mother nucleus are known. For example, JP-A-2001-97949 and JP-A-2003-104976 describe fluorescent compounds having a heterocyclic ring as a basic skeleton, and describe that they are useful as light-emitting elements and wavelength conversion elements. . However, these publications do not show any nonlinear optical phenomenon. Further, the fluorescent compound does not necessarily cause a two-photon absorption phenomenon.
JP 2001-97949 A JP 2003-104976 A Chem. Mater., 10 (7), 1863 (1998) Tetrahedron Lett., 44,8121 (2003) Polymer 44,6851 (2003) Chem.Commun., 2003,2168

  As described above, for the application of two-photon absorption, it is assumed that the two-photon absorption cross section is large, but in order to efficiently use the fluorescence generated by two-photon excitation, the Stokes shift is It must be a large two-photon absorbing compound.

  However, currently available two-photon absorption compounds have a small Stokes shift, so that re-absorption of fluorescence generated by two-photon excitation occurs, and thus there is a disadvantage that the effective utilization efficiency of two-photon emission is low. .

  Therefore, the present invention is a high-efficiency organic nonlinear optical material that has a large two-photon absorption cross section, is likely to cause two-photon absorption, has a large Stokes shift, and can efficiently extract fluorescence generated by two-photon excitation. The purpose is to provide.

（一般式（II）中、環Ａと環Ｚは、炭素原子を２個共有して縮合した環を表し、各々置換基を有していてもよい。）］ The organic nonlinear optical material of the present invention is characterized by containing a compound represented by the following general formula (I) as at least a part of the constituent components.
(Ar ² ) _m -Ar ^1- (Ar ³ ) _n (I)
[In General Formula (I), Ar ¹ represents a divalent heterocyclic group represented by the following General Formula (II), and Ar ² and Ar ³ may each independently have a substituent. A heterocyclic group having aromaticity or an aromatic hydrocarbon ring group, m and n each represent an integer of 1 to 4, and when m and / or n is 2 or more, each of Ar ² and / or Ar ² is 2 or more ³ may be the same as or different from each other, and Ar ² and Ar ¹ , and Ar ¹ and Ar ³ are bonded together in a state in which a conjugated system is connected.

(In general formula (II), ring A and ring Z represent a ring condensed by sharing two carbon atoms, and each may have a substituent.)]

  That is, as a result of intensive studies, the present inventors have solved the above problem by using a compound in which an aromatic hydrocarbon ring or an aromatic heterocyclic ring is bonded to a benzothiadiazole ring or the like via a conjugated system. The inventors have found that this can be solved, and have reached the present invention.

  In the present invention, when the term “heterocycle” or “hydrocarbon ring” is simply used, it includes both a ring having aromaticity and a ring having no aromaticity.

  In the general formula (II), ring Z is a 6-membered ring which may have a substituent, ring A is preferably a 5-membered ring, and general formula (II) is represented by the following general formula (IIa) , (IIb), and among them, those represented by the following general formula (IIa) having an electron-withdrawing 5-membered ring are more preferable.

［一般式（IIａ），（IIｂ）において、環Ｚは一般式（II）における環Ｚと同義の環よりなる２価の基であり、一般式（IIａ）中、Ｙは１６族元素を表し、一般式（IIｂ）中、ＸはＮ又はＳを表す。］
また、Ａｒ^２とＡｒ^３は置換基を有するものが好ましく、特に、Ａｒ^２とＡｒ^１、及びＡｒ^１とＡｒ^３の共役系がつながるような置換基が好ましい。とりわけ、Ａｒ^２とＡｒ^３の少なくとも一方が、置換基としてジ置換アミノ基を有することが好ましく、両方がジ置換アミノ基を有することが特に好ましい。

[In General Formulas (IIa) and (IIb), Ring Z is a divalent group consisting of a ring having the same meaning as Ring Z in General Formula (II). In General Formula (IIa), Y represents a Group 16 element. In general formula (IIb), X represents N or S. ]
Ar ² and Ar ³ preferably have a substituent, and in particular, a substituent that connects a conjugated system of Ar ² and Ar ¹ and Ar ¹ and Ar ³ is preferable. In particular, it is preferable that at least one of Ar ² and Ar ³ has a disubstituted amino group as a substituent, and it is particularly preferable that both have a disubstituted amino group.

  According to such an organic nonlinear optical material of the present invention, an organic nonlinear optical material that exhibits a two-photon absorption phenomenon, a large Stokes shift, and preferably high emission efficiency of 130 nm or more is provided. Particularly preferred is a Stokes shift of 130 to 200 nm.

  According to the present invention, the multiphoton absorption cross-sectional area, particularly the two-photon absorption cross-sectional area is large, two-photon absorption is easily caused, and the Stokes shift is large, so that the fluorescence generated by the two-photon excitation can be efficiently extracted. An organic nonlinear optical material with luminous efficiency is provided.

  Hereinafter, embodiments of the organic nonlinear optical material of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and various modifications are made within the scope of the invention. be able to.

（一般式（II）中、環Ａと環Ｚは、炭素原子を２個共有して縮合した環を表し、各々置換基を有していてもよい。）］ The organic nonlinear optical material of the present invention contains a compound represented by the following general formula (I) as at least a part of the constituent components.
(Ar ² ) _m -Ar ^1- (Ar ³ ) _n (I)
[In General Formula (I), Ar ¹ represents a divalent heterocyclic group represented by the following General Formula (II), and Ar ² and Ar ³ may each independently have a substituent. A heterocyclic group having aromaticity or an aromatic hydrocarbon ring group, m and n each represent an integer of 1 to 4, and when m and / or n is 2 or more, each of Ar ² and / or Ar ² is 2 or more ³ may be the same as or different from each other, and Ar ² and Ar ¹ , and Ar ¹ and Ar ³ are bonded together in a state in which a conjugated system is connected.

(In general formula (II), ring A and ring Z represent a ring condensed by sharing two carbon atoms, and each may have a substituent.)]

In the general formula (I), Ar ¹ preferably has aromaticity.
In the general formula (II), the ring Z is a 5- or 6-membered ring which may have a substituent, a monocyclic ring or a heterocyclic ring or heterocyclic ring having 2 to 6 condensed rings. Can be mentioned. When the ring Z is a heterocycle, the heteroatom constituting the heterocycle is not particularly limited, but usually each atom such as O, S, Se, N, P, Si, preferably O, S, N Particularly preferred is N. When two or more of these heteroatoms are contained in the ring Z, the heteroatoms may be the same atom or different atoms.

  Specific examples of the ring Z include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring, pyridine ring, thiophene ring, pyrrole ring, furan ring, benzothiophene ring, benzofuran ring, benzopyrrole ring, imidazole ring, quinoline A ring, an isoquinoline ring, a carbazole ring, a thiazole ring, a dibenzothiophene ring, and the like. A monocyclic ring is preferable, and a heteroatom such as N such as a 6-membered aromatic hydrocarbon ring such as a benzene ring or a pyridine ring is particularly preferable Is a heterocyclic ring having aromaticity.

  The ring A in the general formula (II) represents a heterocycle optionally having a substituent, which is constituted with two carbon atoms shared with the ring Z, and the heteroatom constituting the heterocycle is particularly limited. Usually, each atom such as O, S, Se, N, P, and Si is used. When two or more of these heteroatoms are contained in ring A, the heteroatoms may be the same or different. Ring A is preferably a heterocyclic ring having aromaticity, and particularly preferably a 5-membered aromatic heterocyclic ring having a heteroatom such as N, S, or O.

  In the general formula (II), examples of the substituent that the ring A and the ring Z may have include the substituents described later as the substituent in the general formulas (IIa) and (IIb).

In particular, Ar ¹ represented by the general formula (II) is a divalent compound composed of two cyclic structures sharing two carbon atoms, represented by any one of the following general formulas (IIa) and (IIb). It is preferably a heterocyclic group, and particularly preferably represented by the following general formula (IIa) having an electron-withdrawing 5-membered ring.

［一般式（IIａ），（IIｂ）において、環Ｚは一般式（II）における環Ｚと同義の環よりなる２価の基であり、一般式（IIａ）中、Ｙは１６族元素を表し、一般式（IIｂ）中、ＸはＮ又はＳを表す。］
上記一般式（IIａ）において、Ｙは好ましくはＯ又はＳである。

[In General Formulas (IIa) and (IIb), Ring Z is a divalent group consisting of a ring having the same meaning as Ring Z in General Formula (II). In General Formula (IIa), Y represents a Group 16 element. In general formula (IIb), X represents N or S. ]
In the general formula (IIa), Y is preferably O or S.

Ar ¹ represented by the general formulas (IIa) and (IIb) may have a substituent, that is, a ring Z or a heterocyclic ring containing a Y atom in the general formula (IIa), the general formula (IIb) As the substituent that the heterocyclic ring containing the X atom in can have, an alkyl group, a hydrocarbon ring group, a heterocyclic group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an aralkyloxy group, a heteroaralkyloxy group, a substituent Examples thereof include an amino group, an acyl group, a nitro group, a cyano group, an ester group, a halogen atom, a hydroxyl group, and a carboxyl group, which may have a group. More specifically, it is derived from an alkyl group having 1 to 9 carbon atoms, a hydrocarbon ring group having 3 to 20 carbon atoms, a 5 or 6-membered monocyclic ring or a 2 to 6 condensed ring as exemplified below. Heterocyclic group, C1-C9 alkoxy group, C2-C18 (hetero) aryloxy group, C3-C18 (hetero) aralkyloxy group, C2-C20 alkylamino group, carbon A (hetero) arylamino group having 2 to 30 carbon atoms, an acyl group having 1 to 20 carbon atoms, a nitro group, a cyano group, an ester group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, and a carboxyl group, preferably Examples include organic groups having 10 or less carbon atoms, particularly electron-withdrawing groups such as a nitro group, a cyano group, an ester group, and a carboxyl group. In particular, a cyano group, an ester group, and a carboxyl group are preferable.

  Examples of the alkyl group having 1 to 9 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, iso-butyl group, sec-butyl group, tert-butyl group, hexyl group and octyl group. .

  Examples of the hydrocarbon ring group having 3 to 20 carbon atoms include a cyclopropyl group, a cyclohexyl group, a tetradecahydroanthranyl group, a phenyl group, an anthranyl group, and a phenanthryl group.

  Examples of the heterocyclic group derived from a 5- or 6-membered monocyclic ring or a 2-6 condensed ring include 1-pyrenyl group, 1-naphthyl group, 2-naphthyl group, 1-phenanthrenyl group, 1-perylenyl group, 2-piperidinyl Group, 2-piperazinyl group, decahydroquinolinyl group, julolidin-9-yl group and the like.

  Examples of the alkoxy group having 1 to 9 carbon atoms include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, iso-butoxy group, sec-butoxy group, tert-butoxy group, hexyloxy group, octyloxy group, etc. Is mentioned.

  Examples of the (hetero) aryloxy group having 2 to 18 carbon atoms include a phenoxy group, a naphthyloxy group, a 2-thienyloxy group, a 2-furyloxy group, and a 2-quinolyloxy group.

  Examples of the (hetero) aralkyloxy group having 3 to 18 carbon atoms include benzyloxy group, phenethyloxy group, naphthylmethoxy group, 2-thienylmethoxy group, 2-furylmethoxy group, and 2-quinolylmethoxy group.

  Examples of the alkylamino group having 2 to 20 carbon atoms include a dimethylamino group, a methylethylamino group, a dibutylamino group, and a dioctylamino group.

  Examples of the (hetero) arylamino group having 2 to 30 carbon atoms include diphenylamino group, dinaphthylamino group, naphthylphenylamino group, ditolylamino group, di (2-thienyl) amino group, di (2-furyl) amino group, A phenyl (2-thienyl) amino group etc. are mentioned.

  Examples of the acyl group having 1 to 20 carbon atoms include formyl group, acetyl group, propionyl group, isobutyryl group, valeryl group, and cyclohexylcarbonyl group.

  Examples of the ester group having 1 to 6 carbon atoms include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, and an isopropoxycarbonyl group.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  In the general formulas (IIa) and (IIb), among the above-described substituents of each ring, adjacent groups may be bonded to form a cyclic structure. Examples of those in which adjacent substituents are bonded to form a cyclic structure include, for example, those in which the substituents of the benzene ring are bonded to the benzene ring of the ring Z in the general formulas (IIa) and (IIb) Examples include phenoxatin, phenothiazine, and phenoxazine ring formed as shown in the structural formula.

Next, Ar ² and Ar ^{3 in} the general formula (I) will be described.
Ar ² and Ar ³ in the general formula (I) are each independently an aromatic heterocyclic group or aromatic hydrocarbon ring group, preferably a 5- or 6-membered monocyclic or 2-6 condensed ring It represents an aromatic hydrocarbon ring group or a heterocyclic group having aromaticity, and these may have a substituent. M and n each independently represents an integer of 1 to 4, and of these, 1 or 2 is particularly preferable. When m and / or n is 2 or more, two or more Ar ² and / or Ar ³ may be the same as or different from each other.

  Here, the aromatic hydrocarbon ring group is preferably a 6-membered monocyclic group or a group derived from 2 to 10 condensed rings. Specific examples include a phenyl group, a naphthyl group, an anthranyl group, a phenanthryl group, a pyrenyl group, and the like, and a phenyl group is particularly preferable.

  On the other hand, examples of the heterocyclic group having aromaticity include a group derived from a monocyclic or 2-10 condensed ring, preferably a 5- or 6-membered ring, particularly preferably a 5-membered ring. Although there is no restriction | limiting in particular as a hetero atom which comprises a heterocyclic ring, Usually, each atoms, such as O, S, Se, N, P, Si, are mentioned. When two or more of these heteroatoms are contained, the heteroatoms may be the same atom or different atoms. A particularly preferred heteroatom is N. Specific examples of the heterocyclic group having aromaticity include furan, thiophene, pyrrole, benzofuran, isobenzofuran, 1-benzothiophene, 2-benzothiophene, indole, isoindole, indolizine, carbazole, xanthene, pyridine, quinoline. , Isoquinoline, phenanthridine, acridine, oxazole, isoxazole, thiazole, isothiazole, furazane, imidazole, pyrazole, benzimidazole, 1,8-naphthyridine, pyrazine, pyrimidine, pyridazine, etc. Among them, a group derived from a thiophene ring is particularly preferable.

These Ar ² and Ar ³ may be the same as or different from each other.

Examples of the substituent that Ar ² and Ar ³ may have include an alkyl group, a hydrocarbon ring group, a heterocyclic group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an aralkyloxy group, and a heteroaralkyloxy group. And an amino group, an acyl group, a nitro group, a cyano group, an ester group, a halogen atom, a hydroxyl group, a carboxyl group and the like which may have a substituent. More specifically, it is derived from an alkyl group having 1 to 9 carbon atoms, a hydrocarbon ring group having 3 to 20 carbon atoms, a 5 or 6-membered monocyclic ring or a 2 to 6 condensed ring as exemplified below. Heterocyclic group, C1-C9 alkoxy group, C2-C18 (hetero) aryloxy group, C3-C18 (hetero) aralkyloxy group, C2-C20 alkylamino group, carbon Examples thereof include a (hetero) arylamino group having 2 to 30 carbon atoms, an acyl group having 1 to 20 carbon atoms, a nitro group, a cyano group, an ester group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, and a carboxyl group.

  Examples of the alkyl group having 1 to 9 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, iso-butyl group, sec-butyl group, tert-butyl group, hexyl group and octyl group. .

  Examples of the hydrocarbon ring group having 3 to 20 carbon atoms include a cyclopropyl group, a cyclohexyl group, a tetradecahydroanthranyl group, a phenyl group, an anthranyl group, and a phenanthryl group.

  Examples of the heterocyclic group derived from a 5- or 6-membered monocyclic ring or a 2-6 condensed ring include 1-pyrenyl group, 1-naphthyl group, 2-naphthyl group, 1-phenanthrenyl group, 1-perylenyl group, 2-piperidinyl Group, 2-piperazinyl group, decahydroquinolinyl group, julolidin-9-yl group and the like.

  Examples of the alkoxy group having 1 to 9 carbon atoms include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, iso-butoxy group, sec-butoxy group, tert-butoxy group, hexyloxy group, octyloxy group, etc. Is mentioned.

  Examples of the (hetero) aryloxy group having 2 to 18 carbon atoms include a phenoxy group, a naphthyloxy group, a 2-thienyloxy group, a 2-furyloxy group, and a 2-quinolyloxy group.

  Examples of the (hetero) aralkyloxy group having 3 to 18 carbon atoms include benzyloxy group, phenethyloxy group, naphthylmethoxy group, 2-thienylmethoxy group, 2-furylmethoxy group, and 2-quinolylmethoxy group.

  Examples of the alkylamino group having 2 to 20 carbon atoms include a dimethylamino group, a methylethylamino group, a dibutylamino group, and a dioctylamino group.

  Examples of the (hetero) arylamino group having 2 to 30 carbon atoms include diphenylamino group, dinaphthylamino group, naphthylphenylamino group, ditolylamino group, di (2-thienyl) amino group, di (2-furyl) amino group, A phenyl (2-thienyl) amino group etc. are mentioned.

  Examples of the acyl group having 1 to 20 carbon atoms include formyl group, acetyl group, propionyl group, isobutyryl group, valeryl group, and cyclohexylcarbonyl group.

  Examples of the ester group having 1 to 6 carbon atoms include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, and an isopropoxycarbonyl group.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Further, in Ar ² and Ar ³ , among the substituents as described above which each ring has, adjacent groups may be bonded to form a cyclic structure. As the one in which adjacent substituents are bonded to form a cyclic structure, for example, the substituents of the benzene ring are bonded to the benzene ring group as Ar ² and Ar ³ , and the above-mentioned phenoxatin, phenothiazine, Those having a phenoxazine ring are exemplified.

Ar ² and Ar ³ preferably have a di-substituted amino group, particularly an alkyl group, an aryl group, particularly a di-substituted amino group substituted with an aryl group having a large electron donating property as a substituent, and Ar ² and Ar ³ are Those that are both substituted with a di-substituted amino group are even more preferred.

In the compound represented by the general formula (I), Ar ² and Ar ³ are bonded in a state where Ar ¹ and the conjugated system are connected to each other. The state in which this conjugated system is connected indicates a state in which π electrons can be delocalized between the bond chains of Ar ² —Ar ¹ —Ar ³ , for example, an aromatic ring (hydrocarbon ring, Ar ² , Ar ³ ). Heterocycle) and Ar ¹ aromatic heterocycle are connected by a single bond, vinylene group, ethynylene group, or the like. Specifically, the single bond, carbon / carbon double bond, carbon / nitrogen double bond, nitrogen / nitrogen double bond, carbon / carbon triple bond, especially the two-photon absorption cross section is large. / A state in which a carbon double bond is included is mentioned.

  Specific examples of the compound represented by the general formula (I) are shown below, but the present invention is not limited to these.

  In addition, among the above exemplified compounds, some compounds have synthetic methods described in the literature as shown in the following table.

  According to such an organic nonlinear optical material of the present invention, a two-photon absorption phenomenon occurs, and the lower limit of the Stokes shift is usually 130 nm, preferably 140 nm, particularly preferably 150 nm, and the upper limit is usually 200 nm. An organic nonlinear optical material excellent in efficiency is provided.

  The organic nonlinear optical material of the present invention may contain only one kind of the compound represented by the general formula (I), or may contain two or more kinds in any combination and in any ratio. There may be.

  The organic nonlinear optical material of the present invention is a compound represented by the above general formula (I), for example, a powdery crystal of the compound represented by the above general formula (I) obtained by various synthesis methods as it is. , As a block or powder, or a solvent such as hexane, toluene, xylene, methylene chloride, chloroform, ether, tetrahydrofuran, ethyl acetate, acetone, 2-butanone, methanol, ethanol, trifluoromethylbenzene, acetic acid, triethylamine, It can be used for various applications as a liquid material dissolved or dispersed in a polymer or gel, or as a thin film obtained by applying such a liquid material to a substrate and then removing the solvent.

  In addition, the organic nonlinear optical material contains the compound represented by the general formula (I), for example, after subjecting the material to treatment such as decomposition and extraction, for example, liquid chromatography-mass spectrometry ( It can be confirmed by analyzing by LC-MS) or nuclear magnetic resonance spectroscopy (NMR).

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to synthesis examples and examples. However, the present invention is not limited to the following examples unless it exceeds the gist.

[Synthesis example]
Synthesis Example 1: Synthesis of Exemplified Compound A-17 4,7-dibromo-2,1,3-benzothiadiazole (46 mg, 0.16 mmol), tetrakistriphenylphosphine palladium (0) (5.5 mg, 0.005 mmol) ) In ethanol (3 mL) and 2 mol / L aqueous sodium carbonate (10 mL) of 4-diphenylaminophenylboronic acid (100 mg, 0.16 mmol) were added dropwise at 60 ° C. to a benzene solution (20 mL). The mixture was stirred at 85 ° C. for 24 hours and the reaction mixture was poured into water (50 mL). Then, it extracted 3 times with toluene (30 mL), and the solvent was distilled off under reduced pressure after drying an organic layer with anhydrous magnesium sulfate. Chloroform-hexane was used as an eluent, and the residue was subjected to column chromatography to obtain an orange powder (50 mg) which is a mixture of the intermediate and compound A-17. 4- [N- (1-naphthyl) -N-phenyl] of this mixture (50 mg) and tetrakistriphenylphosphine palladium (0) (4 mg, 0.003 mmol) in a benzene solution (15 mL) at 60 ° C. under an argon stream. -An ethanol solution (2 mL) of phenylboronic acid (41 mg, 0.14 mmol) and a 2 mol / L sodium carbonate aqueous solution (7 mL) were added dropwise. The mixture was stirred at 85 ° C. for 16 hours and the reaction mixture was poured into water (50 mL). Then, it extracted 3 times with toluene (20 mL), the organic layer was dried with anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was subjected to silica gel column chromatography using a chloroform-triethylamine mixed solvent as an eluent to obtain compound A-17 (8 mg, 12% yield).

The analytical value of this was as follows.
Melting point: 236-238 ° C
Proton - nuclear magnetic resonance spectroscopy ^{(1 H-NMR) (270MHz} , CDCl 3) d 7.06 (t, J = 8.5Hz, 4H, ArH), 7.17-7.32 (m, 20H, ArH), 7.74 (s, 2H , ArH), 7.88 (d, J = 8.5Hz, 4H, ArH)
Fast atom collision ionization mass spectrometry (FAB-MS) (NBA, positive) 622 (M ⁺ )

Synthesis Example 2: Synthesis of Exemplified Compound A-18 4,7-dibromo-2,1,3-benzothiadiazole (197 mg, 0.67 mmol), tetrakistriphenylphosphine palladium (0) (23 mg, 0.02 mmol) An ethanol solution (2 mL) of 4- [N- (1-naphthyl) -N-phenyl] -phenylboronic acid (250 mg, 0.74 mmol) and 2 mol / L carbonic acid in a benzene solution (20 mL) at 60 ° C. under an argon stream. Aqueous sodium solution (10 mL) was added dropwise. The mixture was stirred at 85 ° C. for 12 hours and the reaction mixture was poured into water (100 mL). Then, it extracted 3 times with toluene (30 mL), and the solvent was distilled off under reduced pressure after drying an organic layer with anhydrous magnesium sulfate. The residue was subjected to silica gel column chromatography using chloroform as an eluent to obtain an orange powder (330 mg) which is a mixture of the intermediate and compound A-18. 4- [N- (1-naphthyl) -N-phenyl] of this mixture (330 mg) and tetrakistriphenylphosphine palladium (0) (23 mg, 0.02 mmol) in a benzene solution (30 mL) at 60 ° C. under an argon stream. -An ethanol solution (2 mL) of phenylboronic acid (295 mg, 0.87 mmol) and a 2 mol / L aqueous sodium carbonate solution (15 mL) were added dropwise. The mixture was stirred at 85 ° C. for 12 hours and the reaction mixture was poured into water (150 mL). Then, it extracted 3 times with toluene (30 mL), and the solvent was distilled off under reduced pressure after drying an organic layer with anhydrous magnesium sulfate. The residue was subjected to silica gel column chromatography using chloroform-hexane as an eluent to obtain Compound A-18 (352 mg, yield 73%).

The analytical value of this was as follows.
Infrared absorption spectrum (IR) (KBr) n _max (cm ^-1 ) 1590,1511,1479,1290,825,773
¹ H-NMR (270 MHz, CDCl ₃ ) d 6.98 (t, J = 6.3 Hz, 2H, ArH), 7.12-7.24 (m, 12H, ArH), 7.36-7.53 (m, 8H, ArH), 7.68 (s , 2H, ArH), 7.79-7.84 (m, 6H, ArH), 7.90 (d, J = 8.6Hz, 2H, ArH), 7.99 (d, J = 8.6Hz, 2H)

Synthesis Example 3: Synthesis of the exemplified compound A-21 4,7-dibromo-2,1,3-benzothiadiazole (411 mg, 1.4 mmol), tetrakistriphenylphosphine palladium (0) (49 mg, 0.042 mmol) An ethanol solution (2 mL) of 4-dimethylaminophenylboronic acid (300 mg, 1.82 mmol) and a 2 mol / L sodium carbonate aqueous solution (25 mL) were added dropwise to a benzene solution (50 mL) at 60 ° C. under an argon stream. The mixture was stirred at 85 ° C. for 12 hours and the reaction mixture was poured into water (100 mL). Then, it extracted 3 times with toluene (40 mL), and the solvent was distilled off under reduced pressure after drying an organic layer with anhydrous magnesium sulfate. The residue was recrystallized with a chloroform-hexane mixed solvent to obtain an orange powder (294 mg) as a mixture of the intermediate and compound A-21. 4-Dimethylaminophenylboronic acid (300 mg, 1.82 mmol) was added to a benzene solution (50 mL) of this mixture (294 mg) and tetrakistriphenylphosphine palladium (0) (49 mg, 0.042 mmol) at 60 ° C. under a stream of argon. An ethanol solution (2 mL) and a 2 mol / L sodium carbonate aqueous solution (25 mL) were added dropwise. The mixture was stirred at 85 ° C. for 12 hours and the reaction mixture was poured into water (100 mL). Then, it extracted 3 times with toluene (40 mL), and the solvent was distilled off under reduced pressure after drying an organic layer with anhydrous magnesium sulfate. The residue was recrystallized from a chloroform-hexane mixed solvent to obtain Compound A-21 (239 mg, yield 77%).

The analytical value of this was as follows.
Red needle crystal: melting point 216-219 ° C
IR (KBr) n _max (cm ^-1 ) 1611,1528,1478,1444,1364,1229,1202,1113,811
¹ H-NMR (270 MHz, CDCl ₃ ) d3.04 (s, 6H, CH ₃ ), 6.89 (d, J = 8.5 Hz, 2H, ArH), 7.68 (s, 2H, ArH), 7.91 (d, J = 8.5Hz, 2H, ArH)
FAB-MS (NBA, positive) 374 (M ⁺ )

Synthesis Example 4: Synthesis of Exemplified Compound A-22 Compound A-22 was synthesized in the same manner as in Synthesis Examples 1 and 3.

Synthesis Example 5 Synthesis of Exemplary Compound B-1 After dissolving palladium acetate (56 mg, 0.25 mmol) and o-tolylphosphine (151 mg, 0.5 mmol) in triethylamine (8 mL) under a nitrogen atmosphere, dibromobenzothiadiazole (882 mg, 3 mmol) and styrene (1060 mg, 10.2 mmol) were added and refluxed for 8 hours. The reaction product was poured into 10% by weight hydrochloric acid and extracted with toluene. The organic layer was washed with water and dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was subjected to silica gel column chromatography to obtain orange solid compound B-1 (512 mg, yield 50%).

The measurement results of the NMR spectrum of this compound are as follows.
¹ H-NMR (CDCl ₃ (δ = ppm)): 7.32 (d, 2H, J = 7.0Hz), 7.38-7.43 (4H, m), 7.62-7.70 (8H, m), 8.00 (d, 2H, (J = 16.1Hz)

Synthesis Example 6: Synthesis of Exemplified Compound H-5
Exemplified compound H-5 was synthesized according to the method described in Heterocycles (2002), 56 (1-2), 421-431.

Synthesis Example 7: Synthesis of Exemplified Compounds PN2AP-BT, P2A-BT, and bP-PyO Exemplified Compounds PN2AP-BT, P2A-BT, and bP-PyO were synthesized in the same manner as in Synthesis Examples 1 to 3, respectively.

Synthesis Example 8 Synthesis of Exemplified Compound H-16 Starting Material Ethyl-4,7-bis (5-phenyl-2-thienyl) -1,2,5-oxadiazolo [3,4-c] pyridine-6-carboxy The rates were synthesized by the method described in the literature (Heterocycles (2002), 56 (1-2), 421-431.).

  10% by weight hydroxylation to ethyl-4,7-bis (5-phenyl-2-thienyl) -1,2,5-oxadiazolo [3,4-c] pyridine-6-carboxylate (1000 mg, 1.96 mmol) A mixed solution (50 mL) of ethanol / water of potassium (50:50 (v / v)) was poured. The mixture was heated and stirred for 4 hours with vigorous stirring. The reaction mixture was cooled to room temperature and poured into ice water. Concentrated hydrochloric acid was added dropwise to adjust the pH to 1, and the precipitated crystals were filtered, and 4,7-bis (5-phenyl-2-thienyl) -1,2,5-oxadiazolo [3,4-c] pyridine- 6-carboxylic acid (H-16) (873 mg, yield 92%) was obtained.

The results of mass spectrometry (MS) spectrum measurement of this compound are as follows.
MS (m / e) 481 (M ⁺ )

Synthesis Example 9: Synthesis of Exemplified Compound A-23 The compound in the form of an orange powder was reacted under the same conditions except that 4-dimethylaminophenylboronic acid was changed to 4'-diphenylamino-4-biphenylboronic acid in Synthesis Example 3. A-23 (yield 18%) was obtained.

The analytical value of this was as follows.
Orange powder: melting point 220-222 ° C
IR (KBr) n _max (cm ^-1 ) 3030,1590,1480,1329,1280,816,754
¹ H-NMR (270 MHz, CDCl ₃ ) d7.05 (t, J = 7.1 Hz, 4H, ArH), 7.14-7.33 (m, 20H, ArH), 7.57 (d, J = 8.9 Hz, 4H, ArH) , 7.76 (d, J = 8.4Hz, 4H, ArH), 7.86 (s, 2H, ArH), 8.06 (d, J = 8.4Hz, 4H, ArH)
FAB-MS (NBA, positive) 774 (M ⁺ )
Anal.Calcd for C ₅₄ H ₃₈ N ₄ S: C = 83.69; H = 4.94; N = 7.23
Found: C = 83.70; H = 4.93; N = 7.26

Synthesis Example 10: Synthesis of Exemplary Compound A-24 In Synthesis Example 3, 4,7-dibromo-2,1,3-benzothiadiazole was converted to 4,7-bis (5-bromo-2-thienyl) -2,1,3. -Benzothiadiazole was reacted under the same conditions except that 4-dimethylaminophenylboronic acid was changed to 4'-diphenylamino-4-biphenylboronic acid, and compound A-24 as a red powder (33% yield) Got.

The analytical value of this was as follows.
Red powder: mp 262-264 ° C
IR (KBr) n _max (cm ^-1 ) 1590,1483,1448,1325,1279,835,795,695,515
¹ H-NMR (CDCl ₃ ) d7.00-7.18 (m, 20H, ArH), 7.27-7.37 (m, 6H, ArH), 7.55 (d, J = 8.6Hz, 4H, ArH), 7.86 (s, 2H, ArH), 8.11 (d, J = 4.0Hz, 2H, ArH)
FAB-MS (NBA, positive) 786 (M ⁺ )
Anal.Calcd for C ₅₀ H ₃₄ N ₄ S ₃・ 0.15CHCl ₃ : C = 74.83; H = 4.28; N = 6.96
Found: C = 74.82; H = 4.26; N = 7.05

Synthesis Example 11: Synthesis of Exemplary Compound B-2 The reaction was performed under the same conditions except that styrene was changed to 4-diphenylaminostyrene in Synthesis Example 4 to obtain red crystalline compound B-2 (yield 17%). .

The analytical value of this was as follows.
Red crystals: mp 196-198 ° C
IR (KBr) n _max (cm ^-1 ) 1589,1507,1591,1326,1281,1175,963
¹ H-NMR (CDCl ₃ ) d7.02-7.16 (m, 16H, ArH), 7.27 (d, J = 7.3Hz, 8H, ArH), 7.29 (d, J = 8.6Hz, 4H, ArH), 7.52 (d, J = 8.6Hz, 4H, ArH), 7.54 (d, J = 16.2Hz, 2H, olefinH), 7.65 (s, 2H, ArH), 7.92 (d, J = 16.2Hz, 2H, olefinic H )
FAB-MS (NBA, positive) 674 (M ⁺ )
Anal.Calcd for C ₄₆ H ₃₄ N ₄ S ・ 0.03CHCl ₃ : C = 81.49; H = 5.06; N = 8.26
Found: C = 81.41; H = 5.10; N = 8.21

Synthesis Example 12: Synthesis of Exemplified Compound C-2 A 1 mol / L potassium hydroxide methanol solution (15 mL) of 4,7-bis (trimethylsilylethynyl) -2,1,3-benzothiadiazole (180 mg, 0.54 mmol) at room temperature For 1 hour. The reaction mixture was poured into water (40 mL) and extracted three times with chloroform (25 mL). The organic layer was dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure to obtain 4,7-diethynyl-2,1,3-benzothiadiazole (91 mg, 0.49 mmol) as a brown powder.

  To a tetrahydrofuran solution of 4,7-diethynyl-2,1,3-benzothiadiazole (91 mg, 0.49 mmol), 4-diphenylaminoiodobenzene (400 mg, 1.08 mmol) and triethylamine (2 mL) under an argon stream. Diphenylphosphinoferrocene palladium dichloride (7 mg, 0.01 mmol) and copper iodide were added. The reaction mixture was stirred at room temperature for 1.5 hours, poured into water (50 mL) and extracted three times with methylene chloride (30 mL). The organic layer was neutralized with 1.2 mol / L hydrochloric acid (20 mL), washed with a saturated aqueous sodium chloride solution, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was subjected to silica gel column chromatography to obtain red powder compound C-2 (yield 11%).

The analytical value of this was as follows.
Red powder: mp 249-251 ° C
IR (KBr) n _max (cm ^-1 ) 2198 (Vcc), 1589,1557,1510,1490,1317,1287,1172,824,753
¹ H-NMR (CDCl ₃ ) d7.03 (d, J = 8.9Hz, 4H, ArH), 7.12 (d, J = 8.6Hz, 12H, ArH), 7.26-7.32 (m, 8H, ArH), 7.50 (d, J = 8.9Hz, 4H, ArH), 7.73 (s, 2H, ArH)
FAB-MS (NBA, positive) 670 (M ⁺ )
Anal.Calcd for C ₄₆ H ₃₀ N ₄ S ・ 0.1CHCl ₃ : C = 81.09; H = 4.44; N = 8.20
Found: C = 81.05; H = 4.48; N = 8.07

[Example]
About each compound obtained by the synthesis example, the two-photon absorption cross section, the two-photon excitation fluorescence peak wavelength, and the linear absorption peak wavelength were measured by the following methods, and the results are shown in Table 3.

  Further, the Stokes shift of each compound was calculated by the difference between the two-photon excitation fluorescence peak wavelength and the linear absorption peak wavelength, and the results are shown in Table 3.

<Evaluation method of two-photon absorption cross section>
Two-photon absorption cross-sectional area is evaluated by Guang S. He, Lixiang Yuan, Ning Cheng, Jayant D. Bhawalkar, Paras N. Prasad, Lawrence L. Brott, Stephen J. Clarson, Bruce A. Reinhardt, J. Opt. Soc. Am .B Vol.14, No.5 (1997) pp.1079-1087. A femtosecond titanium sapphire laser (wavelength: 800 nm, pulse width: 100 fs, repetition rate: 1 kHz, average output: 2 W, peak power: 20 GW) is used as a measurement light source, and the output from the laser is appropriately attenuated to absorb two-photons. The cross-sectional area was measured. For the measurement, the Z-scan method was used to change the excitation light density in the range of 1 to 40 GW / cm ² . As a measurement sample, a solution in which each compound was dissolved in toluene at a concentration shown in Table 2 below was used, and this solution was put into a four-side transparent 1 cm square quartz cell for measurement.

<Method for evaluating two-photon excitation fluorescence peak wavelength>
Two-photon excitation fluorescence wavelength evaluation was carried out by a method according to the evaluation method of the two-photon absorption cross section. The same arrangement as the two-photon absorption cross-sectional area was performed up to the part where the sample was irradiated with the laser from the light source. The sample and the sample cell were the same as those used for the two-photon absorption cross section measurement. The sample was excited under the conditions of an excitation light intensity of 10 mW and an excitation light density of 10 GW / cm ² , and the fluorescence generated from the sample was condensed by placing a lens in a direction orthogonal to the incident laser beam, and then the fluorescence spectrum was measured. . The obtained fluorescence spectrum was read for the peak wavelength after correcting the wavelength dependence of the apparatus. The peak wavelength includes an error of ± 1 nm.

<Evaluation method of linear absorption peak wavelength>
For the evaluation of the linear absorption peak wavelength, A-17, 18, 21, 22, B-1, H-5, 16, PN2AP-BT, P2A-BT, bP-PyO are Shimadzu's UV-visible spectrophotometers. Using UV-3100S, A-23 and 24 were each carried out using a spectrophotometer V-570 manufactured by JASCO Corporation. For the measurement sample, a solution in which each compound was dissolved in toluene at the concentration shown in Table 2 below was used. This solution was put in a quartz cell having a cell length of 1 cm, and only toluene was put in the same cell for measurement. did. The peak wavelength includes an error of ± 1 nm.

  From Table 3, it can be seen that the organic nonlinear optical material of the present invention has a large two-photon absorption cross-sectional area, a large Stokes shift, and excellent luminous efficiency.

  The organic nonlinear optical material of the present invention is expected to be applied as a two-photon absorption compound in the fields of optical memory, two-photon modeling, two-photon photodynamic therapy and the like. In particular, since the organic nonlinear optical material of the present invention is excellent in two-photon emission efficiency, application as a light conversion material and a photosensitizer is also expected.

Claims (5)

An organic nonlinear optical material comprising a compound represented by the following general formula (I) as at least a part of a constituent component.
(Ar ² ) _m -Ar ^1- (Ar ³ ) _n (I)
[In General Formula (I), Ar ¹ represents a divalent heterocyclic group represented by the following General Formula (II), and Ar ² and Ar ³ may each independently have a substituent. A heterocyclic group having aromaticity or an aromatic hydrocarbon ring group, m and n each represent an integer of 1 to 4, and when m and / or n is 2 or more, each of Ar ² and / or Ar ² is 2 or more ³ may be the same as or different from each other, and Ar ² and Ar ¹ , and Ar ¹ and Ar ³ are bonded together in a state in which a conjugated system is connected.

(In general formula (II), ring A and ring Z represent a ring condensed by sharing two carbon atoms, and each may have a substituent.)]   In the general formula (II), the ring Z represents a 6-membered ring which may have a substituent, and the ring A represents a 5-membered ring which may have a substituent. The organic nonlinear optical material described in 1. The organic nonlinear optical material according to claim 1, wherein at least one of Ar ² and Ar ³ has a di-substituted amino group as a substituent. The organic nonlinear optical material according to any one of claims 1 to 3, wherein the general formula (II) is represented by the following general formula (IIa).

[In General Formula (IIa), Ring Z is a divalent group consisting of a ring having the same meaning as Ring Z in General Formula (II), and Y represents a Group 16 element. ]   An organic nonlinear optical material which causes a two-photon absorption phenomenon and has a Stokes shift of 130 to 200 nm.