JP4751998B2 - Two-photon absorption material - Google Patents

Description

The present invention relates to a two-photon absorption materials containing organic boron compound π-conjugated hydrocarbon units and boron atoms are bonded.

  Two-photon absorption is a phenomenon in which a molecule transitions from a ground state to an excited state by simultaneously absorbing two photons (photons, Photons) at one time.

  When causing such a transition to the excited state of the molecule, the energy of the two photons may be the same or different. If a storage medium such as an optical memory medium is formed using a material that generates two-photon absorption (hereinafter referred to as “two-photon absorption material”), bit data can be recorded at a predetermined position of the storage medium. . That is, a laser beam having a wavelength corresponding to half of the energy gap between the ground state and the excited state of the storage medium is irradiated to a predetermined position of the storage medium, and the structure of the storage medium is changed by a two-photon absorption process. The derived refractive index change can be caused, and this refractive index change can be stored as bit data at a predetermined position.

  Since the two-photon absorption process occurs in proportion to the square of the light intensity of the incident light, compared to the one-photon absorption process, the spot size due to the change in the refractive index formed at a predetermined position of the storage medium, particularly in the optical axis direction. Can be reduced in size. The ability to suppress the spread of the beam in the direction of the optical axis can be beneficial for realizing high-density three-dimensional optical recording. That is, in a stacked thin film element in which bit data is optically written to each layer, the space of each layer can be made smaller than that of the one-photon type, and as a result, high density can be achieved.

  Conventionally, in order to realize a two-photon absorption type optical storage medium, research and development have been mainly conducted on the following two methods.

(1) A method of using a conventional one-photon absorption type storage material by diverting it to a two-photon absorption type (2) A method of applying a π-electron conjugated molecule developed as a two-photon absorption type Here, the method of (1) Used a photoisomerization material such as azobenzene, spiropyran, diarylethene and the like as a two-photon absorption material (see, for example, Non-Patent Document 1). In the method (2), a third-order nonlinear optical material such as polyacetylene, polydiacetylene, polyarylene vinylene, and porphyrin is used as the two-photon absorption material (see, for example, Non-Patent Document 2).
T.A. SHIONO et al, Japan Journal of Applied Physics, Vol. 44, no. 5B, pp. 3559-3563 (2005) D. Y. KIM et al, Journal of Physical Chemistry, Vol. 109, no. 13, pp. 2996-2999 (2005)

  However, these materials have their respective problems. That is, since the material of the method (1) is not naturally developed as a two-photon absorption material, the two-photon absorption efficiency is low, and optical storage using an inexpensive small laser device cannot be performed. There was a problem that it was not right. Even if the material according to the method (2) is two-photon absorption efficiency is about 1 to 2 orders of magnitude higher than the material according to the method (1), it reaches a sufficient level in consideration of the performance of a practical optical storage medium. In addition, there is a problem that even if the two-photon absorption coefficient is high to some extent, the influence of the thermal effect due to the contribution of one-photon absorption cannot be completely eliminated. Of course, the influence of the thermal effect cannot be eliminated even with the material of the method (1).

  The materials of the methods (1) and (2) have a low solubility in organic solvents, and therefore have a problem that they are not suitable for easily producing a thin film element or the like which is a practical device element. In addition, these material systems have a problem that once they are excited to an excited state, they quickly return to the ground state after light irradiation, and it is difficult to fix the refractive index change as it is. The material used in the method (1) has one of fatal defects caused by expanding the π-conjugated system in order to increase the two-photon absorption coefficient (two-photon absorption efficiency). No ideal material has been found that does not have all of the flaws.

  On the other hand, in the field of theoretical studies on two-photon absorption, when a π-conjugated system with excellent symmetry is expanded or a nitrogen atom is introduced into the π-conjugated system, the empty orbit (LUMO and LUMO + 1LUMO) is near the center of the π-conjugated system. There is a report that orbital distortion increases due to uneven distribution of the occupied orbitals (HOMO and HOMO-1) at the end of the π-conjugated system, thereby increasing the third-order nonlinear optical effect and the two-photon absorption efficiency. It was. Regarding such a phenomenon, a material having a relatively large two-photon absorption coefficient has been found experimentally even though it is a low molecule, but it is insufficient as a guideline for developing a practical material.

  For this reason, the two-photon absorption material has a molecular structure in which a two-photon absorption has a large molecular structure and an excited state caused by the two-photon absorption induces a refractive index change.

  In particular, a molecular structure with a large two-photon absorption had to be realized while avoiding actual excitation due to the expansion of the π-conjugated system as described above and the two-photon absorbing material becoming insoluble in the solvent. .

 The present invention has been made in view of the above circumstances, and an object thereof is to provide an organic boron compound and a two-photon absorption material that have a molecular orbital distortion contributing to the two-photon absorption effect and are soluble in a solvent. .

       In order to avoid actual excitation and insolubilization in a solvent as described above, the present inventors do not simply expand the π-conjugated system, but actively apply molecular orbital distortion that contributes to the two-photon absorption effect. As a result of intensive investigation into introducing a hetero atom into a π-conjugated system to produce a two-photon absorption material containing an organoboron compound in which a boron atom is bonded to a π-conjugated system, The present inventors have found that two-photon absorption efficiency is larger by two digits or more than usual in a wavelength region where there is no real absorption, and π electron distortion is biased, and the present invention has been completed.

       Furthermore, the site | part of the boron atom of the organoboron compound was found to be unstable and easily cleaved as compared with other sites, and the present invention was completed. The fact that the boron atom site is easily cleaved has the feature that bond splitting is caused by light irradiation, and as a result, the refractive index change can be fixed without any other means. .

Two-photon absorption material of the present invention, viewed contains an organic boron compound π-conjugated hydrocarbon units and boron atoms are bonded, the organic boron compound is characterized by being represented by the following formula (4).

(However, in the formula (4), X and X ′ may be the same or different, and the following formula (5) (in the formula (5), o and p represent 0 or 1). , Q represents an integer of 0 or more and 4 or less, A represents the following formula (6) (wherein one hydrogen atom may be substituted with an acyclic substituent); 7) (However, one hydrogen atom may be substituted with an acyclic substituent.); The following formula (8) (However, one hydrogen atom is substituted with an acyclic substituent.) The following formula (9) (however, one hydrogen atom may be substituted with a non-cyclic substituent); the following formula (10) (however, one hydrogen atom) Or may be substituted with an acyclic substituent.); Or the following formula (11) (the broken line represents a double bond as appropriate; J represents an optionally substituted carbon atom or nitrogen atom) , T represents a carbon atom, nitrogen atom, oxygen atom, sulfur atom or single bond which may have a substituent; Q represents a carbon atom which may have a substituent; Represents a nitrogen atom, an oxygen atom or a sulfur atom; M represents an optionally substituted carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a single bond; and L represents an optionally substituted group. Represents a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom; and J and T or T and Q may be combined to form a 1,4-dioxane ring or a benzene ring. A cycloalkyl group having 3 to 10 carbon atoms; an alkenylene group having 2 to 6 carbon atoms; a carbazolyl group; a hydrogen atom substituted with an optionally substituted phenyl group or alkyl group Optionally amino group; pyridini A thiophenyl group which may have a substituent, a phenyl group which may have a substituent, a phenylene group which may have a substituent, and E is one or 2 hydrogen atoms may be substituted with an alkyl group having 1 to 10 carbon atoms; one hydrogen atom is substituted with an alkyl group having 1 to 6 carbon atoms An optionally substituted pyridinyl group; a thiophenyl group in which one hydrogen atom may be substituted with an alkyl group having 1 to 6 carbon atoms; one hydrogen atom having 1 to 6 carbon atoms G represents an alkyl group having 1 to 4 carbon atoms in which a hydrogen atom may be substituted with a halogen atom; a hydrogen atom substituted with a halogen atom 1 or more carbon atoms may be , 12 an alkoxy group, a halogen atom, a cyano group, q number of G may be different even in the same. ). )

The two-photon absorption material of the present invention includes an organic boron compound in which a π-conjugated hydrocarbon unit and a boron atom are bonded, and the organic boron compound is represented by the following formula (20).

(In the formula (20), X and X ′ may be the same or different (provided that X ′ may not be present), and m represents an integer of 2 or more and 10,000 or less, The following formula (21) (where, o and p in formula (21) represent 0 or 1, q represents an integer of 0 or more and 4 or less. A represents the following formula (22) (however, 1 Wherein one hydrogen atom may be substituted with an acyclic substituent.); Formula (23) below (wherein one hydrogen atom may be substituted with an acyclic substituent); The following formula (24) (however, one hydrogen atom may be substituted with a non-cyclic substituent); the following formula (25) (where one hydrogen atom is a non-cyclic substituent) The following formula (26) (however, one hydrogen atom may be substituted with an acyclic substituent); or the following formula ( 27) (The broken line represents a double bond as appropriate; J represents an optionally substituted carbon atom, nitrogen atom, oxygen atom or sulfur atom; T represents an optionally substituted carbon atom. Represents a nitrogen atom, an oxygen atom, a sulfur atom or a single bond; Q represents an optionally substituted carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom; M represents an optionally substituted group; Represents a good carbon atom, nitrogen atom, oxygen atom, sulfur atom or single bond; L represents a carbon atom, nitrogen atom, oxygen atom or sulfur atom which may have a substituent; J and T or T and Q Together may form a 1,4-dioxane ring or a benzene ring.) D represents a cycloalkyl group having 3 to 10 carbon atoms; The following alkenylene group; carbazolyl group; hydrogen atom is a substituent A phenyl group which may have an amino group which may be substituted with an alkyl group; a pyridinyl group; a pyrazinylene group; a thiophenyl group which may have a substituent; a phenyl group which may have a substituent Represents a phenylene group which may have a substituent, and E represents a phenyl group in which one or two hydrogen atoms may be substituted with an alkyl group having 1 to 10 carbon atoms; One hydrogen atom may be substituted with an alkyl group having 1 to 6 carbon atoms; one hydrogen atom is substituted with an alkyl group having 1 to 6 carbon atoms; G represents an alkyl group having 1 to 4 carbon atoms in which a hydrogen atom may be substituted with a halogen atom, and G represents 1 carbon atom in which a hydrogen atom may be substituted with a halogen atom. More than 12 Alkoxy group, a halogen atom, a cyano group, q number of G may be different even in the same. ). )

In the two-photon absorption material of the present invention, J represents an optionally substituted carbon atom, nitrogen atom or sulfur atom, and T represents an optionally substituted carbon atom, nitrogen atom or single bond. Q represents an optionally substituted carbon atom, nitrogen atom or sulfur atom, and M preferably represents an optionally substituted carbon atom, nitrogen atom or single bond.

In the two-photon absorption material of the present invention, A represents the following formula (36) (wherein one hydrogen atom is an alkyl having 1 to 4 carbon atoms in which the hydrogen atom may be substituted with a halogen atom) A group; an alkoxy group having 1 to 12 carbon atoms in which a hydrogen atom may be substituted with a halogen atom; a phenyl group in which a hydrogen atom may have an alkyl group having 1 to 2 carbon atoms Or an amino group optionally substituted by an alkyl group having 1 to 2 carbon atoms; -B (Mes) ₂ (However, Mes is represented by the following formula (37).); —Si (CH ₃ ) ₃ -Si (C ₆ H ₅ ) ₃ Cyano group; optionally substituted with a halogen atom; ) Is preferable.

In the two-photon absorption material of the present invention, A is represented by the following formula (38) (wherein one hydrogen atom is an alkyl having 1 to 4 carbon atoms in which the hydrogen atom may be substituted with a halogen atom) A hydrogen atom may be substituted with a halogen atom, and may be substituted with an alkoxy group having 1 to 4 carbon atoms.

In the two-photon absorption material of the present invention, A is represented by the following formula (39) (wherein one hydrogen atom is an alkyl having 1 to 4 carbon atoms in which the hydrogen atom may be substituted with a halogen atom) It may be substituted with a group .

In the two-photon absorption material of the present invention, A represents the following formula (40) (provided that one hydrogen atom is an alkyl having 1 to 4 carbon atoms in which the hydrogen atom may be substituted with a halogen atom) It may be substituted with a group.

In the two-photon absorption material of the present invention, A represents the following formula (41) (wherein one hydrogen atom is an alkyl having 1 to 8 carbon atoms in which the hydrogen atom may be substituted with a halogen atom) It may be substituted with a group.

In the two-photon absorption material of the present invention, A is represented by the following formula (42) (however, the nitrogen atom may be substituted with an alkyl group having 1 to 4 carbon atoms). Is preferred.

In the two-photon absorption material of the present invention, A is represented by the following formula (43) (however, the nitrogen atom may be substituted with an alkyl group having 1 to 4 carbon atoms). Is preferred.

In the two-photon absorption material of the present invention, A is represented by the following formula (44) (however, the nitrogen atom may be substituted with an alkyl group having 1 to 4 carbon atoms). Is preferred.

In the two-photon absorption material of the present invention, D is a cycloalkyl group having 3 to 6 carbon atoms; an alkenylene group having 2 to 3 carbon atoms; an alkyl group having 1 to 10 carbon atoms; or A phenyl group which may be substituted with an alkoxy group having 1 to 3 carbon atoms; a phenyl group in which one hydrogen atom may be substituted with an alkyl group having 1 to 4 carbon atoms, or An amino group which may be substituted with an alkyl group having 1 to 4 carbon atoms; a thiophenyl group in which one hydrogen atom may be substituted with an alkyl group having 1 to 4 carbon atoms; It preferably represents a phenylene group.

In the two-photon absorption material of the present invention, E is a phenyl group in which one or two hydrogen atoms may be substituted with an alkyl group having 1 to 8 carbon atoms; It preferably represents a thiophenyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms.

In the two-photon absorption material of the present invention, G preferably represents a methyl group in which a hydrogen atom may be substituted with a halogen atom; an n-hexoxy group.

In the two-photon absorption material of the present invention, in the above formulas (4) and (20), X and X ′ are preferably represented by any of the following formulas (45) to (114).

In the two-photon absorption material of the present invention, in the above formula (4) and formula (20), X is represented by formula (116), X ′ is represented by formula (117), or X is represented by formula (118), X ′ is represented by formula (119), or X is represented by formula (120), X ′ is represented by formula (121), or X is represented by formula (122), and X ′ is represented by formula (123). It is preferable that X is represented by the formula (124) and X ′ is represented by the formula (125).

  Since the two-photon absorption material of the present invention contains an organic boron compound in which a π-conjugated hydrocarbon unit and a boron atom are bonded, the bond in the vicinity of the boron atom is selectively broken by irradiation with ultraviolet light. Therefore, if an optical storage medium is produced using the two-photon absorption material of the present invention, and the bond breaks in the optical storage medium by the two-photon absorption process, the size of the optical storage medium can be increased by reducing the spot size and making it three-dimensional. Capacitance can be achieved. In addition, by using the two-photon absorption process, it is possible to reduce the beam spot, so that three-dimensional optical writing to the optical storage medium is facilitated. Moreover, the two-photon absorption material and the organic boron compound of the present invention are soluble in various organic solvents.

  Hereinafter, the two-photon absorption material and the organoboron compound of the present invention will be described in detail.

  The two-photon absorption material of the present invention contains an organic boron compound in which a π-conjugated hydrocarbon unit and a boron atom are bonded.

  The organoboron compound is preferably represented by the following formula (126) or formula (127).

However, in the above formula (126) and formula (127), R ₂ and R ₃ represent an alkyl group, aryl group or heteroaryl group having 2 or more carbon atoms.

  Examples of the alkyl group having 2 or more carbon atoms include an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a 2-butyl group, a t-butyl group, a 2-methylbutyl group, and a 3-methylbutyl group. , A cyclohexylmethyl group, a neopentyl group, a 2-ethylbutyl group, a 2-butyl group, a cyclohexyl group, a 3-pentyl group, or a linear, branched, or cyclic alkyl group. Among these, Preferably, it is a C2-C12 alkyl group, Most preferably, it is a C3-C12 branched alkyl group.

  As the aryl group or heteroaryl group, for example, an aryl group such as phenyl group, naphthyl group, anthranyl group, fluorenyl group, phenanthryl group; thiophenyl group, pyridyl group, furanyl group, pyrrolyl group, benzimidazolyl group, imidazolyl group, Examples include heteroaryl groups such as pyrazoyl groups. Of these, a monocyclic or condensed bimembered (hetero) aryl group having about 6 to 12 carbon atoms is preferred. Among these, a monocyclic (hetero) aryl group is particularly preferable.

Further, in the above formula (126) and _(127), a benzene ring having R 2, _{R 3 may} further have a substituent other than R 2, _{R 3.}

Specific examples of the substituent that the benzene ring having R ₂ and R ₃ may further have include those listed as specific examples of R ₂ and R ₃ above.

Hereinafter, as the following formula (128) to formula (133), the structure of the benzene ring having R ₂ and R ₃ is specifically exemplified, but the present invention is limited to these as long as the gist thereof is not exceeded. It is not a thing. In the following formulas (128) to (131), Me represents a methyl group.

  Further, in the above formula (126) and formula (127), X and X ′ are represented by the following general formula (134). X and X ′ may be the same or different. However, X ′ may not be present. k or l X may be the same or different. k and l represent an integer of 1 or more and 10,000 or less.

  In the above general formula (134), o and p represent 0 or 1, and q represents an integer of 0 or more and 4 or less. Ar represents an aryl group or heteroaryl group in which one or more hydrogen atoms may be substituted with an acyclic substituent.

  Specific examples of the aromatic ring constituting the aryl group or heteroaryl group include a 5-membered monocyclic ring, a furan ring, a thiophene ring, a pyrrole ring, an imidazole ring, a thiazole ring, an oxadiazole ring, and a 6-membered monocyclic ring. Examples of the benzene ring, pyridine ring, pyrazine ring and condensed ring include naphthalene ring, phenanthrene ring, pyrene ring, quinoline ring, isoquinoline ring, quinoxaline ring, benzofuran ring, carbazole ring, dibenzothiophene ring and anthracene ring.

  D represents a cycloalkyl group having 3 or more and 10 or less carbon atoms; an alkenylene group having 2 or more and 6 or less carbon atoms; a carbazolyl group; a phenyl group or an alkyl group in which a hydrogen atom may have a substituent. An optionally substituted amino group; a pyridinyl group; a pyrazinylene group; a thiophenyl group optionally having a substituent; a phenyl group optionally having a substituent; a phenylene group optionally having a substituent. Represents.

  E represents a phenyl group in which one or two hydrogen atoms may be substituted with an alkyl group having 1 to 10 carbon atoms; one hydrogen atom has 1 to 6 carbon atoms A pyridinyl group optionally substituted with an alkyl group; one hydrogen atom may be a thiophenyl group optionally substituted with an alkyl group having 1 to 6 carbon atoms; one hydrogen atom has a carbon number A thiophenylene group which may be substituted with 1 or more and 6 or less alkyl groups;

  G represents an alkyl group having 1 to 4 carbon atoms in which a hydrogen atom may be substituted with a halogen atom; an alkoxy group having 1 to 12 carbon atoms in which a hydrogen atom may be substituted with a halogen atom A halogen atom; a cyano group, and q G's may be the same or different.

  Further, the organic boron compound is more preferably represented by the following formula (135), formula (136), formula (137), or formula (138).

  However, in the above formula (136), X and X ′ may be the same or different, and the following formula (139) (however, in formula (139), o and p are 0 or 1). Q represents an integer of 0 or more and 4 or less, A represents the following formula (140) (wherein one hydrogen atom may be substituted with an acyclic substituent); (141) (However, one hydrogen atom may be substituted with an acyclic substituent.); The following formula (142) (However, one hydrogen atom is substituted with an acyclic substituent.) The following formula (143) (wherein one hydrogen atom may be substituted with a non-cyclic substituent); the following formula (144) (where one hydrogen is substituted) The atom may be substituted with an acyclic substituent.); Or the following formula (145) (the broken line represents a double bond as appropriate; J represents a substituent) Represents an optionally substituted carbon atom, nitrogen atom, oxygen atom or sulfur atom; T represents an optionally substituted carbon atom, nitrogen atom, oxygen atom, sulfur atom or single bond; and Q represents a substituted group. An optionally substituted carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom; M represents an optionally substituted carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a single bond; L represents an optionally substituted carbon atom, nitrogen atom, oxygen atom or sulfur atom; J and T or T and Q together form a 1,4-dioxane ring or a benzene ring. May be present).

  However, in said formula (137), X and X 'may be the same or different (however, X' may not be present), and m represents an integer of 2 or more and 10,000 or less. In the formula (139), o and p represent 0 or 1, q represents an integer of 0 or more and 4 or less. A represents the following formula (140) (provided that One hydrogen atom may be substituted with an acyclic substituent.); Formula (141) below (provided that one hydrogen atom may be substituted with an acyclic substituent) The following formula (142) (provided that one hydrogen atom may be substituted with an acyclic substituent); the following formula (143) (provided that one hydrogen atom is acyclic substitution); The following formula (144) (however, one hydrogen atom may be substituted with a non-cyclic substituent): Or the following formula (145) (the broken line represents a double bond as appropriate; J represents an optionally substituted carbon atom, nitrogen atom, oxygen atom or sulfur atom; T represents a substituent); Represents an optionally substituted carbon atom, nitrogen atom, oxygen atom, sulfur atom or single bond; Q represents an optionally substituted carbon atom, nitrogen atom, oxygen atom or sulfur atom; M represents a substituted atom; An optionally substituted carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a single bond; L represents an optionally substituted carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom; J and T or T and Q may be combined to form a 1,4-dioxane ring or a benzene ring.

  However, in said formula (138), X and X 'may be the same or different (however, X' may not be present), and n represents an integer of 2 or more and 10,000 or less. In the formula (139), o and p represent 0 or 1, q represents an integer of 0 or more and 4 or less. A represents the following formula (140) (provided that One hydrogen atom may be substituted with an acyclic substituent.); Formula (141) below (provided that one hydrogen atom may be substituted with an acyclic substituent) The following formula (142) (provided that one hydrogen atom may be substituted with an acyclic substituent); the following formula (143) (provided that one hydrogen atom is acyclic substitution); The following formula (144) (however, one hydrogen atom may be substituted with a non-cyclic substituent): Or the following formula (145) (the broken line represents a double bond as appropriate; J represents an optionally substituted carbon atom, nitrogen atom, oxygen atom or sulfur atom; T represents a substituent); Represents an optionally substituted carbon atom, nitrogen atom, oxygen atom, sulfur atom or single bond; Q represents an optionally substituted carbon atom, nitrogen atom, oxygen atom or sulfur atom; M represents a substituted atom; An optionally substituted carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a single bond; L represents an optionally substituted carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom; J and T or T and Q may be combined to form a 1,4-dioxane ring or a benzene ring.

  D represents a cycloalkyl group having 3 or more and 10 or less carbon atoms; an alkenylene group having 2 or more and 6 or less carbon atoms; a carbazolyl group; a phenyl group or an alkyl group in which a hydrogen atom may have a substituent. An optionally substituted amino group; a pyridinyl group; a pyrazinylene group; a thiophenyl group optionally having a substituent; a phenyl group optionally having a substituent; a phenylene group optionally having a substituent. Represents.

  E represents a phenyl group in which one or two hydrogen atoms may be substituted with an alkyl group having 1 to 10 carbon atoms; one hydrogen atom has 1 to 6 carbon atoms A pyridinyl group optionally substituted with an alkyl group; one hydrogen atom may be a thiophenyl group optionally substituted with an alkyl group having 1 to 6 carbon atoms; one hydrogen atom has a carbon number A thiophenylene group which may be substituted with 1 or more and 6 or less alkyl groups;

  G represents an alkyl group having 1 to 4 carbon atoms in which a hydrogen atom may be substituted with a halogen atom; an alkoxy group having 1 to 12 carbon atoms in which a hydrogen atom may be substituted with a halogen atom A halogen atom; a cyano group, and q G's may be the same or different.

A is represented by the above formula (140), formula (141), formula (142), formula (143), formula (144), and one hydrogen atom is substituted with an acyclic substituent The substituent is an alkyl group having 1 to 10 carbon atoms in which hydrogen atoms may be substituted with halogen atoms; 1 to 12 carbon atoms in which hydrogen atoms may be substituted with halogen atoms An alkoxy group; a hydrogen atom, a phenyl group which may have an alkyl group having 1 to 4 carbon atoms, or an amino group optionally substituted with an alkyl group having 1 to 4 carbon atoms Group; halogen atom and the like. As such a substituent, for example, —CH ₃ , —CH ₂ CH ₃ , — (CH ₂ ) ₂ CH ₃ , — (CH ₂ ) ₃ CH ₃ , — (CH ₂ ) ₄ CH ₃ , — (CH _{2) 5 CH 3, - (} CH 2) 6 CH 3, - (CH 2) 7 CH 3, - (CH 2) 8 CH 3, - (CH 2) 9 CH 3, -OCH 3, -OCH 2 CH ₃ , —O (CH ₂ ) ₂ CH ₃ , —O (CH ₂ ) ₃ CH ₃ , —O (CH ₂ ) ₄ CH ₃ , —O (CH ₂ ) ₅ CH ₃ , —O (CH ₂ ) ₆ CH ₃ , —O (CH ₂ ) ₇ CH ₃ , —O (CH ₂ ) ₈ CH ₃ , —O (CH ₂ ) ₉ CH ₃ , —O (CH ₂ ) ₁₀ CH ₃ , —O (CH ₂ ) ₁₁ CH ₃ , —CF ₃ , —CF ₂ CF ₃ , — (CF ₂ ) ₂ CF ₃ , — (CF ₂ ) ₃ CF ₃ ,-(CF ₂ ) ₄ CF ₃ ,-(CF ₂ ) ₅ CF ₃ ,-(CF ₂ ) ₆ CF ₃ ,-(CF ₂ ) ₇ CF ₃ ,-(CF ₂ ) ₈ CF ₃ ,-(CF _{2) 9 CF 3, -OCF 3} , -OCF 2 CF 3, -O (CF 2) 2 CF 3, -O (CF 2) 3 CF 3, -O (CF 2) 4 CF 3, -O (CF _{2) 5 CF 3, -O (} CF 2) 6 CF 3, -O (CF 2) 7 CF 3, -O (CF 2) 8 CF 3, -O (CF 2) 9 CF 3, -O (CF ₂ ) ₁₀ CF ₃ , —O (CF ₂ ) ₁₁ CF ₃ , —B (Mes) ₂ (where Mes is a methicyl group (2,4,6-trimethylphenyl group) represented by the following formula (146) ) represents _{a), -. Si (CH 3} ) 3, -Si (C 6 H 5) 3, cyano group, fluorine Chlorine, bromine, and the like.

In addition, when A is represented by the above formula (140), among the above substituents, a hydrogen atom may be substituted with a halogen atom, an alkyl group having 1 to 4 carbon atoms; a hydrogen atom Is an alkoxy group having 1 or more and 4 or less carbon atoms that may be substituted with a halogen atom; a hydrogen atom is a phenyl group or carbon that may have an alkyl group having 1 or more and 2 or less carbon atoms An amino group which may be substituted with an alkyl group having a number of 1 or more and 2 or less; -B (Mes) ₂ ; -Si (CH ₃ ) ₃ ; -Si (C ₆ H ₅ ) ₃ ; cyano group; halogen atom Etc. are preferable. As such a substituent, for example, —CH ₃ , —CH ₂ CH ₃ , — (CH ₂ ) ₂ CH ₃ , — (CH ₂ ) ₃ CH ₃ , —OCH ₃ , —OCH ₂ CH ₃ , —O _{(CH 2) 2 CH 3,} -O (CH 2) 3 CH 3, -CF 3, -CF 2 CF 3, - (CF 2) 2 CF 3, - (CF 2) 3 CF 3, -OCF 3, _{-OCF 2 CF 3, -O (CF} 2) 2 CF 3, -O (CF 2) 3 CF 3, -B (Mes) 2, -Si (CH 3) 3, -Si (C 6 H 5) 3 , Cyano group, fluorine and the like.

When A is represented by the above formula (141), among the above substituents, a hydrogen atom may be substituted with a halogen atom, an alkyl group having 1 to 4 carbon atoms; An alkoxy group having 1 to 4 carbon atoms which may be substituted with atoms is preferred. As such a substituent, for example, —CH ₃ , —CH ₂ CH ₃ , — (CH ₂ ) ₂ CH ₃ , — (CH ₂ ) ₃ CH ₃ , —OCH ₃ , —OCH ₂ CH ₃ , —O _{(CH 2) 2 CH 3,} -O (CH 2) 3 CH 3, -CF 3, -CF 2 CF 3, - (CF 2) 2 CF 3, - (CF 2) 3 CF 3, -OCF 3, _{-OCF 2 CF 3, -O (CF} 2) 2 CF 3, etc. -O _{(CF 2) 3} CF 3 and the like.

When A is represented by the above formula (142), among the above substituents, an alkyl group having 1 to 4 carbon atoms in which a hydrogen atom may be substituted with a halogen atom is preferable. As such a substituent, for example, —CH ₃ , —CH ₂ CH ₃ , — (CH ₂ ) ₂ CH ₃ , — (CH ₂ ) ₃ CH ₃ , —CF ₃ , —CF ₂ CF ₃ , — ( _{CF 2) 2 CF 3, -} (CF 2) such as 3 CF ₃ and the like.

When A is represented by the above formula (143), among the above substituents, an alkyl group having 1 to 4 carbon atoms in which a hydrogen atom may be substituted with a halogen atom is preferable. As such a substituent, for example, —CH ₃ , —CH ₂ CH ₃ , — (CH ₂ ) ₂ CH ₃ , — (CH ₂ ) ₃ CH ₃ , —CF ₃ , —CF ₂ CF ₃ , — ( _{CF 2) 2 CF 3, -} (CF 2) such as 3 CF ₃ and the like.

When A is represented by the above formula (144), among the above substituents, an alkyl group having 1 to 8 carbon atoms in which a hydrogen atom may be substituted with a halogen atom is preferable. As such a substituent, for example, —CH ₃ , —CH ₂ CH ₃ , — (CH ₂ ) ₂ CH ₃ , — (CH ₂ ) ₃ CH ₃ , — (CH ₂ ) ₄ CH ₃ , — (CH _{2) 5 CH 3, - (} CH 2) 6 CH 3, - (CH 2) 7 CH 3, -CF 3, -CF 2 CF 3, - (CF 2) 2 CF 3, - (CF 2) 3 CF _{3, - (CF 2) 4} CF 3, - (CF 2) 5 CF 3, - (CF 2) 6 CF 3, - (CF 2) such as 7 CF ₃ and the like.

  Moreover, when A is represented by said Formula (145), J represents the carbon atom which may have a substituent, a nitrogen atom, or a sulfur atom, and T may have a substituent. Represents a carbon atom, a nitrogen atom or a single bond, Q represents an optionally substituted carbon atom, a nitrogen atom or a sulfur atom, and M represents an optionally substituted carbon atom, nitrogen atom or It preferably represents a single bond. Examples of such A include, for example, a phenyl group which may have a substituent; a pyridinyl group which may have a substituent; a thiophenyl group which may have a substituent; A furanyl group which may have a substituent; a pyridazinyl group which may have a substituent; a pyrimidinyl group which may have a substituent; a pyrazinyl group which may have a substituent.

Further, A represents the following formula (147) (wherein one hydrogen atom may be substituted with an alkyl group having 1 to 4 carbon atoms in which the hydrogen atom may be substituted with a halogen atom). Preferably). In this case, examples of the substituent include —CH ₃ , —CH ₂ CH ₃ , — (CH ₂ ) ₂ CH ₃ , — (CH ₂ ) ₃ CH ₃ , —CF ₃ , —CF ₂ CF ₃ , — ( _{CF 2) 2 CF 3, -} (CF 2) such as 3 CF ₃ and the like.

A represents the following formula (148) (wherein one hydrogen atom may be substituted with an alkyl group having 1 to 8 carbon atoms in which the hydrogen atom may be substituted with a halogen atom). ) Is preferable. In this case, examples of the substituent include —CH ₃ , —CH ₂ CH ₃ , — (CH ₂ ) ₂ CH ₃ , — (CH ₂ ) ₃ CH ₃ , — (CH ₂ ) ₄ CH ₃ , — (CH _{2) 5 CH 3, - (} CH 2) 6 CH 3, - (CH 2) 7 CH 3, -CF 3, -CF 2 CF 3, - (CF 2) 2 CF 3, - (CF 2) 3 CF _{3, - (CF 2) 4} CF 3, - (CF 2) 5 CF 3, - (CF 2) 6 CF 3, - (CF 2) such as 7 CF ₃ and the like.

A is preferably represented by the following formula (149) (wherein the nitrogen atom may be substituted with an alkyl group having 1 to 4 carbon atoms). In this case, examples of the substituent include —CH ₃ , —CH ₂ CH ₃ , — (CH ₂ ) ₂ CH ₃ , — (CH ₂ ) ₃ CH ₃ , —CF ₃ , —CF ₂ CF ₃ , — ( _{CF 2) 2 CF 3, -} (CF 2) such as 3 CF ₃ and the like.

A is preferably represented by the following formula (150) (wherein the nitrogen atom may be substituted with an alkyl group having 1 to 4 carbon atoms). In this case, examples of the substituent include —CH ₃ , —CH ₂ CH ₃ , — (CH ₂ ) ₂ CH ₃ , — (CH ₂ ) ₃ CH ₃ , —CF ₃ , —CF ₂ CF ₃ , — ( _{CF 2) 2 CF 3, -} (CF 2) such as 3 CF ₃ and the like.

A is preferably represented by the following formula (151) (wherein the nitrogen atom may be substituted with an alkyl group having 1 to 4 carbon atoms). In this case, examples of the substituent include —CH ₃ , —CH ₂ CH ₃ , — (CH ₂ ) ₂ CH ₃ , — (CH ₂ ) ₃ CH ₃ , —CF ₃ , —CF ₂ CF ₃ , — ( _{CF 2) 2 CF 3, -} (CF 2) such as 3 CF ₃ and the like.

D represents a cycloalkyl group having 3 to 6 carbon atoms; an alkenylene group having 2 to 3 carbon atoms; an alkyl group having 1 to 10 carbon atoms; or an alkyl group having 1 to 10 carbon atoms; A phenyl group optionally substituted with 3 or less alkoxy groups; one hydrogen atom may be substituted with an alkyl group having 1 to 4 carbon atoms, or 1 to 4 carbon atoms An amino group which may be substituted with the following alkyl group; preferably a thiophenyl group where one hydrogen atom may be substituted with an alkyl group having 1 to 4 carbon atoms; a thiophenylene group. . Such D, for _{example, -CH = CH -, - CH} = C = CH -, - N (CH 3) 2, -N (CH 2 CH 3) 2, -N (CH 2 CH 2 CH 3 ) ₂ , —N (CH ₂ CH ₂ CH ₂ CH ₃ ) ₂ , and those represented by the following formulas (152) to (183).

  E represents a phenyl group in which one or two hydrogen atoms may be substituted with an alkyl group having 1 to 8 carbon atoms; one hydrogen atom has 1 to 4 carbon atoms It preferably represents a thiophenyl group that may be substituted with an alkyl group. Examples of such E include those represented by the above formulas (156) to (163), those represented by the above formulas (180) to (183), and the following formulas (184) to (191). ) And the like.

G preferably represents a methyl group in which a hydrogen atom may be substituted with a halogen atom; an n-hexoxy group. Such G, for _{example, -CF 3, -CCl 3, -CBr} 3, and the like _{-O (CH 2) 5 CH 3} .

  In the above formula (137), m is an integer of 2 or more and 10000 or less, and is preferably 4 or more and 500 or less because of excellent solubility in various solvents and easy handling.

  Similarly, in the above formula (138), n is an integer of 2 or more and 10000 or less, and is preferably 4 or more and 500 or less from the viewpoint of excellent solubility in various solvents and easy handling.

  Among such organic boron compounds, in the above formula (135), formula (136), formula (137), and formula (138), X and X ′ are preferably represented by the following formula (192). .

  Similarly, in the above formula (135), formula (136), formula (137), and formula (138), X and X ′ are preferably represented by the following formula (193).

  In the above formula (135), formula (136), formula (137), and formula (138), X and X ′ are preferably represented by the following formula (194).

  In the above formula (135), formula (136), formula (137), and formula (138), X and X ′ are preferably represented by the following formula (195).

  In the above formula (135), formula (136), formula (137), and formula (138), X and X ′ are preferably represented by the following formula (196).

  In the above formula (135), formula (136), formula (137), and formula (138), X and X ′ are preferably represented by the following formula (197).

  In the above formula (135), formula (136), formula (137), and formula (138), X and X ′ are preferably represented by the following formula (198).

  In the above formula (135), formula (136), formula (137), and formula (138), X and X ′ are preferably represented by the following formula (199).

  In the above formula (135), formula (136), formula (137), and formula (138), X and X ′ are preferably represented by the following formula (200).

  In the above formula (135), formula (136), formula (137), and formula (138), X and X ′ are preferably represented by the following formula (201).

  In the above formula (135), formula (136), formula (137), and formula (138), it is preferable that X and X ′ are represented by the following formula (202).

  In the above formula (135), formula (136), formula (137), and formula (138), X and X ′ are preferably represented by the following formula (203).

  In the above formula (135), formula (136), formula (137), and formula (138), X and X ′ are preferably represented by the following formula (204).

  In the above formula (135), formula (136), formula (137), and formula (138), X and X ′ are preferably represented by the following formula (205).

  In the above formula (135), formula (136), formula (137), and formula (138), X and X ′ are preferably represented by the following formula (206).

  In the above formula (135), formula (136), formula (137), and formula (138), X and X ′ are preferably represented by the following formula (207).

  In the above formula (135), formula (136), formula (137), and formula (138), X and X ′ are preferably represented by the following formula (208).

  In the above formula (135), formula (136), formula (137), and formula (138), X and X ′ are preferably represented by the following formula (209).

  In the above formula (135), formula (136), formula (137), and formula (138), it is preferable that X and X ′ are represented by the following formula (210).

  In the above formula (135), formula (136), formula (137), and formula (138), X and X ′ are preferably represented by the following formula (211).

  In the above formula (135), formula (136), formula (137), and formula (138), X and X ′ are preferably represented by the following formula (212).

  In the above formula (135), formula (136), formula (137), and formula (138), X and X ′ are preferably represented by the following formula (213).

  In the above formula (135), formula (136), formula (137), and formula (138), X and X ′ are preferably represented by the following formula (214).

  In the above formula (135), formula (136), formula (137), and formula (138), X and X ′ are preferably represented by the following formula (215).

  In the above formula (135), formula (136), formula (137), and formula (138), X and X ′ are preferably represented by the following formula (216).

  In the above formula (135), formula (136), formula (137), and formula (138), X and X ′ are preferably represented by the following formula (217).

  In the above formula (135), formula (136), formula (137), and formula (138), X and X ′ are preferably represented by the following formula (218).

  In the above formula (135), formula (136), formula (137), and formula (138), X and X ′ are preferably represented by the following formula (219).

  In the above formula (135), formula (136), formula (137), and formula (138), X and X ′ are preferably represented by the following formula (220).

  In the above formula (135), formula (136), formula (137), and formula (138), X and X ′ are preferably represented by the following formula (221).

  In the above formula (135), formula (136), formula (137), and formula (138), X and X ′ are preferably represented by the following formula (222).

  In the above formula (135), formula (136), formula (137), and formula (138), X and X ′ are preferably represented by the following formula (223).

  In the above formula (135), formula (136), formula (137), and formula (138), X and X ′ are preferably represented by the following formula (224).

  In the above formula (135), formula (136), formula (137), and formula (138), X and X ′ are preferably represented by the following formula (225).

  In the above formula (135), formula (136), formula (137), and formula (138), it is preferable that X and X ′ are represented by the following formula (226).

  In the above formula (135), formula (136), formula (137), and formula (138), it is preferable that X and X ′ are represented by the following formula (227).

  In the above formula (135), formula (136), formula (137), and formula (138), X and X ′ are preferably represented by the following formula (228).

  In the above formula (135), formula (136), formula (137), and formula (138), X and X ′ are preferably represented by the following formula (229).

  In the above formula (135), formula (136), formula (137), and formula (138), it is preferable that X and X ′ are represented by the following formula (230).

  In the above formula (135), formula (136), formula (137), and formula (138), X and X ′ are preferably represented by the following formula (231).

  In the above formula (135), formula (136), formula (137), and formula (138), it is preferable that X and X ′ are represented by the following formula (232).

  In the above formula (135), formula (136), formula (137), and formula (138), X and X ′ are preferably represented by the following formula (233).

  In the above formula (135), formula (136), formula (137), and formula (138), X and X ′ are preferably represented by the following formula (234).

  In the above formula (135), formula (136), formula (137), and formula (138), X and X ′ are preferably represented by the following formula (235).

  In the above formula (135), formula (136), formula (137), and formula (138), X and X ′ are preferably represented by the following formula (236).

  In the above formula (135), formula (136), formula (137), and formula (138), X and X ′ are preferably represented by the following formula (237).

  In the above formula (135), formula (136), formula (137), and formula (138), X and X ′ are preferably represented by the following formula (238).

  In the above formula (135), formula (136), formula (137), and formula (138), X and X ′ are preferably represented by the following formula (239).

  In the above formula (135), formula (136), formula (137), and formula (138), X and X ′ are preferably represented by the following formula (240).

  In the above formula (135), formula (136), formula (137), and formula (138), X and X ′ are preferably represented by the following formula (241).

  In the above formula (135), formula (136), formula (137), and formula (138), X and X ′ are preferably represented by the following formula (242).

  In the above formula (135), formula (136), formula (137), and formula (138), X and X ′ are preferably represented by the following formula (243).

  In Formula (135), Formula (136), Formula (137), and Formula (138), X and X ′ are preferably represented by the following Formula (244).

  In the above formula (135), formula (136), formula (137), and formula (138), it is preferable that X and X ′ are represented by the following formula (245).

  In the above formula (135), formula (136), formula (137), and formula (138), X and X ′ are preferably represented by the following formula (246).

  In the above formula (135), formula (136), formula (137), and formula (138), X and X ′ are preferably represented by the following formula (247).

  In the above formula (135), formula (136), formula (137), and formula (138), X and X ′ are preferably represented by the following formula (248).

  In the above formula (135), formula (136), formula (137), and formula (138), X and X ′ are preferably represented by the following formula (249).

  In the above formula (135), formula (136), formula (137), and formula (138), X and X ′ are preferably represented by the following formula (250).

  In the above formula (135), formula (136), formula (137), and formula (138), it is preferable that X and X ′ are represented by the following formula (251).

  In the above formula (135), formula (136), formula (137), and formula (138), X and X ′ are preferably represented by the following formula (252).

  In the above formula (135), formula (136), formula (137), and formula (138), X and X ′ are preferably represented by the following formula (253).

  In the above formula (135), formula (136), formula (137), and formula (138), X and X ′ are preferably represented by the following formula (254).

  In the above formula (135), formula (136), formula (137), and formula (138), it is preferable that X and X ′ are represented by the following formula (255).

  In the above formula (135), formula (136), formula (137), and formula (138), X and X ′ are preferably represented by the following formula (256).

  In the above formula (135), formula (136), formula (137), and formula (138), X and X ′ are preferably represented by the following formula (257).

  In the above formula (135), formula (136), formula (137), and formula (138), X and X ′ are preferably represented by the following formula (258).

  In the above formula (135), formula (136), formula (137), and formula (138), X and X ′ are preferably represented by the following formula (259).

  In the above formula (135), formula (136), formula (137), and formula (138), it is preferable that X and X ′ are represented by the following formula (260).

  In the above formula (135), formula (136), formula (137), and formula (138), it is preferable that X and X ′ are represented by the following formula (261).

  In the above formula (135), formula (136), formula (137), and formula (138), X is represented by the following formula (263), and X ′ is represented by the following formula (264). preferable.

  In the above formula (135), formula (136), formula (137), and formula (138), X is represented by the following formula (265), and X ′ is represented by the following formula (266). preferable.

  In the above formula (135), formula (136), formula (137), and formula (138), X is represented by the following formula (267), and X ′ is represented by the following formula (268). preferable.

  In the above formula (135), formula (136), formula (137), and formula (138), X is represented by the following formula (269), and X ′ is represented by the following formula (270). preferable.

  In the above formula (135), formula (136), formula (137), and formula (138), X is represented by the following formula (271), and X ′ is represented by the following formula (272). preferable.

  The organoboron compound contained in such a two-photon absorption material of the present invention has a π-conjugated structure that is extended through an empty p-orbital of boron as a π-conjugated skeleton, and further exhibits two-photon absorption. In order to more effectively control the distortion of molecular orbitals caused by boron atoms contributing to the structure, electron donating groups and electron withdrawing groups are provided in the molecule. And the organic boron compound contained in the two-photon absorption material of the present invention selectively breaks the bond in the vicinity of the boron atom when irradiated with ultraviolet light (by a one-photon process). Therefore, if an optical storage medium is produced using the two-photon absorption material of the present invention, and the bond breaks in the optical storage medium by the two-photon absorption process, the size of the optical storage medium can be increased by reducing the spot size and making it three-dimensional. Capacitance can be achieved. Furthermore, when using the two-photon absorption process, compared to the case of the one-photon absorption process, the spread of the focused spot of the beam, especially in the direction of the optical axis, is significantly shortened, enabling a smaller spot. Therefore, three-dimensional optical writing to the optical storage medium is facilitated.

  Moreover, the organoboron compound contained in the two-photon absorption material of the present invention is soluble in various organic solvents. As the organic solvent for dissolving the organic boron compound, a benzene-based organic solvent having a large structure correlation with the molecular structure of the compound is preferably used. As the benzene-based organic solvent, toluene, xylene, mesitylene (trimethylbenzene), Examples thereof include diethylbenzene and isopropylbenzene. In addition, among the compounds, when a substituent having an electron donating property, a hetero atom or the like is added to the molecule, polar solvents such as chloroform, methylene chloride, acetone, dioxane, ethyl acetate, and tetrahydrofuran are used as preferred solvents. Can be added as: Further, when the compound is dispersed in a polymer medium, a polar solvent such as N-methylpyrrolidone, dimethylformamide, dimethylacetamide, trimethyl phosphate, or methyl ethyl ketone may be used in the case of a highly polar polymer. it can. However, since these polar solvents easily contain moisture, care must be taken to use them in a dehydrated state. This is because the compound can be decomposed not only by light but also by water.

  This organoboron compound is formed in a thin film on a substrate made of various insulating materials, and this thin film is used as a two-photon absorption material.

  In order to form the organoboron compound in a thin film on a substrate, first, the organoboron compound is dissolved in the organic solvent as described above to prepare a solution containing the organoboron compound.

  Next, this solution is applied onto a substrate by a spin coating method or the like and then dried to obtain a thin film made of an organic boron compound.

  Next, with reference to FIG. 1, the 1st example of the manufacturing method of an organoboron compound is shown.

  Here, the case where X and X ′ in the above formula (136) are phenyl groups as the organic boron compound will be described.

  After putting magnesium (Mg) into a four-necked flask, a three-way cock connected to a nitrogen line is attached, and nitrogen substitution in this four-necked flask and drying under reduced pressure are performed.

Next, dehydrated tetrahydrofuran (hereinafter abbreviated as “THF”) was dropped into the four-necked flask, and then 1,2-dibromoethane was added thereto and stirred. Dehydrated THF in which bromo-2,4,6 - triisopropylbenzene (compound (α) shown in FIG. 1) is dissolved is slowly added dropwise.

  After the dropwise addition of dehydrated THF in which the compound (α) is dissolved, the four-necked flask is reacted at 78 ° C. for 2 hours in an oil bath, and then allowed to cool at room temperature.

  In the same manner as described above, after nitrogen substitution in another four-necked flask and drying under reduced pressure, trimethoxyborane (Trimethoxyborane) was put into this four-necked flask, and the ice-bath was added. Cool to -10 ° C.

  Then, after slowly dropping the reaction solution obtained by reacting the above compound (α) into the four-necked flask charged with this trimethoxyborane, the reaction solution in the four-necked flask was reacted for 1 hour. Raise to room temperature.

  Next, the reaction liquid in the four-necked flask is filtered by suction, the crystals contained in the reaction liquid are washed with dehydrated pentane, and all the filtrate is concentrated to obtain a transparent oil.

  The obtained oil is distilled under reduced pressure to obtain the compound (β) shown in FIG.

  In addition, a three-way cock connected to a nitrogen line is attached to another four-necked flask, and nitrogen substitution in this four-necked flask and vacuum drying are performed.

  Next, the compound (β), dehydrated ether and dehydrated pentane are charged into the four-necked flask and stirred while cooling to 0 ° C. with an ice bath.

Next, a 20% ether solution of lithium aluminum hydride (LiAlH ₄ ) is dropped into the four-necked flask and reacted at 0 ° C. for 1.5 hours.

  Next, after raising the temperature of the reaction solution in the four-necked flask to room temperature, the filtrate is transferred to another dry four-necked flask while filtering the reaction solution through a glass filter.

  Next, trimethylchlorosilane (TMSCl) is dropped into the four-necked flask to which the reaction solution has been transferred, and is reacted at room temperature for 2 hours.

  Next, while filtering the reaction solution in the four-necked flask through a glass filter, the filtrate is transferred into another dry four-necked flask.

  Thereafter, the reaction solution transferred into the four-necked flask is concentrated while heating and decompressing to obtain the compound (γ) shown in FIG.

  Next, after dehydrating THF was introduced into a four-necked flask containing the compound (γ) to prepare a solution, 4-ethynyl-N, N′-dimethylaniline (4-Ethynyl-N, N′— Dimethylylline) is added and stirred while warming at 40 ° C. for 5 hours in a water bath.

  Next, after concentrating the reaction solution in the four-necked flask while heating and reducing the pressure, the concentrate in the four-necked flask is crystallized by adding cold hexane, and this crystal is washed with cold hexane. To obtain the compound (δ) shown in FIG.

  Next, with reference to FIG. 2, the 2nd example of the manufacturing method of an organoboron compound is shown.

 Here, the case where X and X ′ in the above formula (136) are represented by the above formula (206) will be described as the organoboron compound.

 A four-necked flask is equipped with a three-way cock connected to a nitrogen line, and nitrogen substitution in the four-necked flask and vacuum drying are performed.

  Next, the compound (β), dehydrated ether and dehydrated pentane are charged into the four-necked flask and stirred while cooling to 0 ° C. with an ice bath.

  Next, a 20% ether solution of lithium aluminum hydride is dropped into the four-necked flask and reacted at 0 ° C. for 2 hours.

  Next, after raising the temperature of the reaction solution in the four-necked flask to room temperature, the filtrate is transferred to another dry four-necked flask while filtering the reaction solution through a glass filter.

  Next, trimethylsilyl chloride is dropped into the four-necked flask to which the reaction solution has been transferred, and the mixture is reacted at room temperature for 2 hours.

  Next, while filtering the reaction solution in the four-necked flask through a glass filter, the filtrate is transferred into another dry four-necked flask.

 Thereafter, the reaction solution transferred into the four-necked flask is concentrated while heating and decompressing to obtain a compound (γ).

  Next, after dehydrating THF was introduced into a four-necked flask containing the compound (γ) to prepare a solution, 4-ethynyl-N, N′-dimethylaniline (4-Ethynyl-N, N′— Dimethylylline) is added and stirred while warming at 40 ° C. for 5 hours in a water bath.

 Next, after concentrating the reaction solution in the four-necked flask while heating and reducing the pressure, the concentrate in the four-necked flask is crystallized by adding cold hexane, and this crystal is washed with cold hexane. The compound (ε) shown in FIG. 2 is obtained.

  Next, with reference to FIG. 3, the 3rd example of the manufacturing method of an organoboron compound is shown.

 Here, a case where the organic boron compound is represented by the above formula (138) will be described.

 A four-necked flask is equipped with a three-way cock connected to a nitrogen line, and nitrogen substitution in the four-necked flask and vacuum drying are performed.

  Next, the compound (ζ) shown in FIG. 3 and dehydrated THF are introduced into the four-necked flask.

  Next, a compound (γ) is dissolved in dehydrated THF to prepare a solution. This solution is dropped into a four-necked flask containing the compound (ζ), and then reacted at room temperature with stirring for 5 hours. .

  Then, after concentrating the reaction solution in the four-necked flask while heating and reducing the pressure, the concentrate in the four-necked flask is dissolved in a small amount of chloroform and then reprecipitated in methanol.

  Thereafter, the resulting precipitate is dissolved in benzene and freeze-dried to obtain the compound (η) shown in FIG. In the chemical formula representing the compound (η), r is an integer of 2 or more and 10,000 or less.

  Next, with reference to FIG. 4, the 4th example of the manufacturing method of an organoboron compound is shown.

  Here, a case where the organic boron compound is represented by the above formula (138) will be described.

 A four-necked flask is equipped with a three-way cock connected to a nitrogen line, and nitrogen substitution in the four-necked flask and vacuum drying are performed.

  Next, the compound (θ) and dehydrated THF shown in FIG. 4 are charged into the four-necked flask.

  Next, the compound (γ) is dissolved in dehydrated THF to prepare a solution. This solution is dropped into the four-necked flask containing the compound (θ), and then reacted at room temperature with stirring for 12 hours. .

  Then, after concentrating the reaction solution in the four-necked flask while heating and reducing the pressure, the concentrate in the four-necked flask is crystallized by adding cold hexane, and this crystal is washed with cold hexane. The compound (ι) shown in FIG. 4 is obtained. In the chemical formula representing the compound (ι), s is an integer of 2 or more and 10,000 or less.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example.

Example 1
As the organic boron compound, a compound in which X and X ′ in the above formula (136) are phenyl groups was synthesized.

  After putting 3.48 g of magnesium into a four-necked flask with a capacity of 300 mL, a three-way cock connected to a nitrogen line was attached, and nitrogen substitution in this four-necked flask and drying under reduced pressure were performed.

  Next, 10 mL of dehydrated THF was dropped into the four-necked flask, and then 1,2-dibromoethane was added and stirred. After confirming that bubbles were generated, 1-bromo-2,4,6-isopropyl was used. Dehydrated THF in which benzene (compound (α) shown in FIG. 1) was dissolved was slowly added dropwise.

  After completion of the dropwise addition of dehydrated THF in which the compound (α) was dissolved, this four-necked flask was reacted while being heated at 78 ° C. for 2 hours in an oil bath, and then allowed to cool at room temperature.

  Further, in the same manner as described above, after nitrogen substitution and vacuum drying in another 300 mL four-necked flask were performed, 30 mL of trimethoxyborane was introduced into this four-necked flask, and an ice bath was added. To -10 ° C.

  Then, after slowly dropping the reaction solution obtained by reacting the above compound (α) into the four-necked flask charged with this trimethoxyborane, the reaction solution in the four-necked flask was reacted for 1 hour. The temperature was raised to room temperature.

  Next, the reaction liquid in the four-necked flask was filtered with suction, the crystals contained in the reaction liquid were washed with 100 mL of dehydrated pentane, and the filtrate was all concentrated to obtain a transparent oil.

  The obtained oil was distilled under reduced pressure to obtain the compound (β) shown in FIG.

  The resulting compound (β) had a boiling point of 106 to 108 ° C. (1 mmHg), a yield of 10.8 g, and a yield of 36%.

  In addition, a three-way cock connected to a nitrogen line was attached to another four-necked flask with a volume of 100 mL, and nitrogen substitution in this four-necked flask and vacuum drying were performed.

  Next, the compound (β), dehydrated ether 80 mL and dehydrated pentane 20 mL were charged into the four-necked flask and stirred while cooling to 0 ° C. with an ice bath.

  Next, 11 mL of a 20% ether solution of lithium aluminum hydride was dropped into the four-necked flask and reacted at 0 ° C. for 1.5 hours.

  Subsequently, after raising the temperature of the reaction solution in the four-necked flask to room temperature, the filtrate was transferred to another dry 100-mL four-necked flask while filtering the reaction solution through a glass filter.

  Next, 1.4 mL of trimethylchlorosilane was dropped into the four-necked flask to which the reaction solution was transferred, and reacted at room temperature for 2 hours.

  Next, while filtering the reaction solution in the four-necked flask through a glass filter, the filtrate was transferred into another dry four-necked flask having a volume of 100 mL.

  Thereafter, the reaction solution transferred into the four-necked flask was concentrated while warming and decompressing to obtain the compound (γ) shown in FIG. 1 as white crystals.

  Next, in a four-necked flask containing the compound (γ), 22 mL of dehydrated THF was added to prepare a solution, and then 2.0 g of 4-ethynyl-N, N′-dimethylaniline was added, The mixture was stirred at 40 ° C. for 5 hours while warming.

  Next, after concentrating the reaction solution in the four-necked flask while heating and reducing the pressure, the concentrate in the four-necked flask is crystallized by adding cold hexane, and this crystal is washed with cold hexane. As a result, a yellow crystal compound (δ) shown in FIG. 1 was obtained.

  The yield of the obtained compound (δ) was 1.75 g.

Further, when the compound (δ) was analyzed by ¹ H-NMR, 7.59 (d, 4H) ppm, 7.30-7.45 (m, 10H) ppm, 7.00 (s, 2H) ppm, Peaks were observed at 2.95 (m, 1H) ppm, 2.50 (m, 2H) ppm, 1.33 (d, 6H) ppm, and 1.13 (d, 12H) ppm (solvent: deuterium). Chloroform, reference material: tetramethylsilane, frequency 400 MHz). The analysis results are shown in FIG.

  Therefore, it was confirmed that the obtained compound was definitely the compound (δ).

  In addition, compound (δ) was analyzed by a mass spectrometer. The analysis results are shown in FIG.

  As a result of analysis, the weight average molecular weight (Mw) of the compound (δ) was 420.44.

(Example 2)
As the organic boron compound, a compound in which X and X ′ in the above formula (136) are the above formula (206) was synthesized.

 A four-necked flask with a capacity of 100 mL was equipped with a three-way cock connected to a nitrogen line, and the nitrogen in the four-necked flask was replaced and dried under reduced pressure.

  Next, the compound (β), dehydrated ether 45 mL and dehydrated pentane 11 mL were charged into the four-necked flask, and stirred while cooling to 0 ° C. with an ice bath.

  Next, 5.0 mL of a 20% ether solution of lithium aluminum hydride was dropped into the four-necked flask and reacted at 0 ° C. for 2 hours.

  Subsequently, after raising the temperature of the reaction solution in the four-necked flask to room temperature, the filtrate was transferred to another dry 100-mL four-necked flask while filtering the reaction solution through a glass filter.

  Next, 0.48 mL of trimethylsilyl chloride (Trimethylsilyl chloride) was dropped into the four-necked flask to which the reaction solution was transferred, and reacted at room temperature for 2 hours.

  Next, while filtering the reaction solution in the four-necked flask through a glass filter, the filtrate was transferred into another dry four-necked flask.

 Thereafter, the reaction solution transferred into the four-necked flask was concentrated while warming and decompressing to obtain a white crystalline compound (γ).

  Next, in a four-necked flask containing the compound (γ), 22 mL of dehydrated THF was added to prepare a solution, and then 1.45 g of 4-ethynyl-N, N′-dimethylaniline was added, The mixture was stirred at 40 ° C. for 5 hours while warming.

  Next, after concentrating the reaction solution in the four-necked flask while heating and reducing the pressure, the concentrate in the four-necked flask is crystallized by adding cold hexane, and this crystal is washed with cold hexane. As a result, a yellow crystal compound (ε) shown in FIG. 2 was obtained.

  The yield of the obtained compound (ε) was 0.73 g.

Further, when the compound (ε) was analyzed by ¹ H-NMR, 7.47 (d, 4H) ppm, 7.22 (d, 2H) ppm, 7.11 (d, 2H) ppm, 6.98 ( s, 2H) ppm, 6.66 (d, 4H) ppm, 2.99 (s, 12H) ppm, 2.96 (m, 1H) ppm, 2.58 (m, 2H) ppm, 1.32 ( Peaks were observed at d, 6H) ppm and 1.1 (d, 12H) ppm (solvent: deuterated chloroform, reference material: tetramethylsilane, frequency 400 MHz). The analysis results are shown in FIG.

  Therefore, it was confirmed that the obtained compound was definitely the compound (ε).

  Further, the compound (ε) was analyzed by a mass spectrometer. The analysis results are shown in FIG.

  As a result of analysis, the weight average molecular weight (Mw) of the compound (ε) was 506.57.

(Example 3)
As the organic boron compound, the compound represented by the above formula (138) was synthesized.

 A four-necked flask with a capacity of 100 mL was equipped with a three-way cock connected to a nitrogen line, and the nitrogen in the four-necked flask was replaced and dried under reduced pressure.

  Next, in this four-necked flask, 0.03785 g of the compound (ζ) shown in FIG. 3 was dissolved in 1.0 mL of dehydrated THF to prepare a solution.

  Next, 0.6 mL of a tripyrborane tetrahydrofuran solution (0.525M) prepared by dissolving the compound (γ) in dehydrated THF was dropped into the four-necked flask containing the above solution over 30 minutes. Then, the reaction was carried out at room temperature for 5 hours with stirring.

  Thereafter, the reaction liquid in the four-necked flask was concentrated while warming and decompressing, and then the concentrate in the four-necked flask was dissolved in a small amount of chloroform and then reprecipitated in methanol.

  Thereafter, the resulting precipitate was dissolved in benzene and freeze-dried to obtain a polymer compound (η) shown in FIG.

  The yield of the obtained polymer compound (η) was 36%.

When the polymer compound (η) was analyzed by ¹ H-NMR, 7.21-7.69 (8H, Ar—H, B—CH═CH) ppm, 6.92-7.08 (2H, Ar— H (tripyl group)) ppm, 2.86-3.00 (1H, CH (tripyl group)) ppm, 2.39-3.00 (2H, CH (tripyl group)) ppm, 1.02-1. A peak was observed at 41 (18H, CH ₃ (tripyl group)) ppm (solvent: deuterated chloroform, reference substance: tetramethylsilane, frequency 400 MHz).

Further, when the polymer compound (η) was analyzed by ¹³ C-NMR, it was found that 153.1 (Ar) ppm, 149.3 (Ar) ppm, 147.8 (Ar) ppm, 138.7 (Ar (tripyl group) )) Ppm, 135.1 (Ar (tripyl group)) ppm, 132.3 (Ar (tripyl group)) ppm, 127.2-128.8 (-CH = CH-) ppm, 119.8 (-CH = CH-) ppm, 34.8-35.6 (-CH- ) ppm, 34.3 (-CH-) ppm, 23.8-24.9 (-CH 2 -) peak was observed in ppm (Solvent: deuterated chloroform, reference material: tetramethylsilane, frequency 100 MHz).

  Therefore, it was confirmed that the obtained compound was definitely a polymer compound (η).

Example 4
As the organic boron compound, the compound represented by the above formula (138) was synthesized.

 A four-necked flask with a capacity of 100 mL was equipped with a three-way cock connected to a nitrogen line, and the nitrogen in the four-necked flask was replaced and dried under reduced pressure.

  Next, 0.163 g of the compound (θ) shown in FIG. 4 and dehydrated THF were charged into the four-necked flask.

  Next, 0.114 g of the compound (γ) is dissolved in 1 mL of dehydrated THF to prepare a solution. This solution is dropped into the four-necked flask containing the compound (θ), and then stirred at room temperature for 12 hours. It was made to react.

  Then, after concentrating the reaction solution in the four-necked flask while heating and reducing the pressure, the concentrate in the four-necked flask is crystallized by adding cold hexane, and this crystal is washed with cold hexane. The compound (ι) shown in FIG. 4 was obtained as yellow crystals.

  The yield of the obtained polymer compound (ι) was 0.192 g, and the yield was 71%.

  The results of elemental analysis were 81.22 carbon (theoretical value 81.89) and 10.29 hydrogen (theoretical value 10.22), which were in good agreement with the theoretical value.

When the polymer compound (ι) was analyzed by ¹ H-NMR, 7.81 (2H, —CH═CH—) ppm, 6.97 (4H, Ar) ppm, 4.00 to 3.75 (4H, _{-OCH 2 -) ppm, 2.89 (} 3H, Ar-CH ( Toripiru group)) ppm, 2.49 (3H, Ar-CH ( Toripiru group)) ppm, 1.82-0.86 (31H, - C ₅ H ₁₁ -, - peak CCH ₃ (Toripiru group)) ppm were observed (solvent: deuterated chloroform, reference: tetramethylsilane, frequency 400 MHz).

Further, when the polymer compound (ι) was analyzed by ¹³ C-NMR, 151.72 (Ar) ppm, 121.81 (Ar) ppm, 110.63 (Ar) ppm, 148.96 (Ar (tripyl group) )) ppm, 147.236 (Ar (Toripiru group)) ppm, 119.30 (Ar ( Tripyl)) ppm, 129.05 (-CH = CH-) ppm, 69.02 (-OCH 2 -) ppm, 35.00 (—CH—) ppm, 34.31 (—CH—) ppm, 29.24 (—CH ₂ —) ppm, 28.81 (—CH ₂ —) ppm, 25.59 (—CH ₂ — _{) ppm, 22.51 (-CH 2 -} ) ppm, 24.56 (-CH 3 ( Toripiru _{group)) ppm, 14.01 (-CH 3} ) peaks ppm was observed (solvent: deuterated chloroform Reference substance: tetramethyl silane, frequency 100 MHz).

  Therefore, it was confirmed that the obtained compound was definitely a polymer compound (ι).

  Using the thin film made of the compound obtained in the example, bond breakage due to light irradiation based on the one-photon absorption process was examined.

  After the compound (δ) obtained in Example 1 was dispersed in ZEONEX (manufactured by ZEON Corporation), this dispersion was applied onto the substrate by a spin coating method to form a thin film composed of the compound (δ). . The content of the compound (δ) in the obtained thin film was 1.02% by weight, and the thickness of the thin film was 3.5 μm.

Bond breakage is measured by emitting light with a wavelength of 365 nm from a normal UV irradiation apparatus, irradiating the spin coat thin film, and measuring an absorption spectrum in a wavelength range of 240 nm to 510 nm with an absorption spectrum measurement apparatus. It was. At this time, the power of irradiation light was set to 15 mW / cm ² .

  The time change of the absorption spectrum accompanying UV light irradiation is shown in FIG.

  From FIG. 9, it was observed that the absorption peak near the wavelength of 340 nm significantly decreased with the passage of time, while the absorption peak near the wavelength of 270 nm increased. This decrease or increase in the absorption peak corresponds to the fact that bond breakage is caused by UV light irradiation in the compound (δ), thereby shortening the π-electron conjugate length in the molecule. Absorption at a wavelength of 340 nm is derived from the structure of the compound (δ) itself, and absorption near the wavelength of 270 nm is derived from a molecular structure shortened by bond breaking of the compound (δ). Bond breaking is assumed to occur in the vicinity of the boron atom.

  By utilizing the result of the absorption spectrum change based on the above one-photon absorption process, it is possible to lead to bond breakage based on the two-photon absorption process. That is, if the wavelength of the illuminating light source is doubled by the mechanism shown in FIG. 10 (wavelength 700 to 800 nm), it can be conceived that bond breakage can be caused not by the one-photon absorption process but by the two-photon absorption process. . Although FIG. 10 shows a case where the compound (δ) is excited by light absorption of two wavelengths having different wavelengths and bond breakage occurs, light having the same wavelength may be irradiated. In the compound (δ), almost no one-photon absorption is observed at a wavelength of 700 to 800 nm.

  In order to confirm this, the present inventors constructed a white light pump / probe system shown in FIG.

  In FIG. 11, reference numeral 10 is a white light pump / probe system, 11 is a titanium sapphire laser, 12 is a xenon lamp (continuous light), 13 and 14 are reflecting mirrors, 15 and 16 are condensing lenses, 17 is a detector, 18 Indicates a sample (thin film), 19 indicates pump light, and 20 indicates probe light.

  In this system, the sample 18 is irradiated with titanium sapphire laser light (wavelength 796 nm, pulse width 130 fs, repetition frequency 1 kHz) which is pump light 19 emitted from the titanium sapphire laser 11, so that the light generated in the sample 18 is emitted. Changes in absorption (absorbance) can be investigated at once from a wavelength of about 330 nm to about 550 nm by white light (continuous light) that is the probe light 20. When bond breakage occurs in the sample 18, it is possible to detect the change in the absorption peak associated therewith by the detector 17.

  FIG. 12 shows the results of examining the time change of the absorption spectrum based on the two-photon absorption process using the spin coat thin film made of the compound (δ).

The intensity of the pump light was 13.6 mJ · cm ⁻² · pulse ⁻¹ . The concentration of the compound (δ) is 9.9% by weight, and the film thickness is 3.0 μm. As shown in FIG. 12, it was confirmed that the intensity of the absorption peak in the vicinity of the wavelength of 340 nm gradually decreased by light irradiation with a wavelength of 796 nm as well as light irradiation with a wavelength of 365 nm shown in FIG. This result means that, according to the mechanism shown in FIG. 10, irradiation with titanium sapphire laser light caused bond breakage in the molecule due to the two-photon absorption process, resulting in a shortened π-electron conjugate length. FIG. 13 shows the results of plotting the time dependence of absorbance at wavelengths from 350 nm to 360 nm on average. It was found that the absorbance monotonously decreases in proportion to the irradiation time. It was found that, due to the two-photon absorption process, the excited state was excited in proportion to the irradiation time, and bond breakage occurred as it was.

  An experiment was conducted to verify that the results shown in FIGS. 12 and 13 were due to the two-photon absorption process, not the one-photon absorption process.

FIG. 14 is a schematic diagram showing an experimental system. The experiment was performed by using a semiconductor-excited solid laser with a wavelength of 660 nm as pump light, a GaN laser with a wavelength of 410 nm as probe light, and examining the change in transmittance of the probe light with a detector. The intensity of the pump light incident on the sample was 20 mW (100 W / cm ² ), and the intensity of the probe light was 7 nW (35 mW / cm ² ). The reason why the probe light power is set to a low value of 7 nW is to prevent a change in transmittance due to the incidence of the probe light itself.

  The results are shown in FIG.

For reference, the result of using a GaN laser with a wavelength of 410 nm as the pump light is also shown in the same experimental system. The power of the GaN laser in this case was set to 500 mW (50 mW / cm ² ). In light irradiation with a wavelength of 410 nm, the transmittance gradually increases even at a wavelength of 410 nm in response to a decrease in the absorption peak peculiar to the polymer (corresponding to a decrease in the absorption peak in FIG. 9). Then, it turned out that the transmittance | permeability in wavelength 410nm hardly changes. Even in the same experiment in which the pump light wavelength was set to 830 nm and the light intensity was set to five times that in the case of the pump light wavelength of 660 nm, the transmittance change hardly occurred as in FIG. If bond breakage occurs due to the one-photon absorption process at wavelengths of 660 nm and 830 nm, considering the overwhelming difference in efficiency from the two-photon absorption process (it is estimated to be several digits or more), FIG. A change in transmittance should be seen.

  In addition, although the above result used ZEONEX as a dispersion medium of a compound ((delta)), the same result was obtained also with polymethylmethacrylate (PMMA).

  Again, the results show that the organoboron compound is a material that does not cause one-photon absorption, i.e., can eliminate the thermal effect, in the wavelength region of 660 nm and 830 nm.

  The same experiment as FIG. 13 was conducted by the experimental system shown in FIG. 11 using the spin coat thin film prepared by dispersing the compound (ε) obtained in Example 2 in ZEONEX (manufactured by Nippon Zeon Co., Ltd.). .

The concentration of the compound (ε) is 9.8% by weight, and the film thickness is 3.0 μm. The intensity of the pump light was 13.6 mJ · cm ⁻² · pulse ⁻¹ . In FIG. 16, the result of having averaged the time dependence of the light absorbency in wavelength 350nm to 360nm is plotted.

  As a result, also in the compound (ε), irradiation with titanium sapphire laser light caused bond breakage in the molecule due to the two-photon absorption process, which means that the π-electron conjugate length was shortened. The absorbance decreased monotonously in proportion to the irradiation time in the same manner as in the compound (δ), but the manner (ratio) of the decrease was 2-3% greater than that in the compound (δ). This is also influenced by the way of taking the wavelength range in which the absorbance is averaged, but it is presumed that the molecular structure of the compound (ε) is also related. That is, the compound (ε) has the same basic structure as that of the compound (δ), and a dimethylamino group is added to increase the π-electron conjugation length. It can be thought that this brought about a change.

  Even when the spin coat thin film made of the polymer compound (η) obtained in Example 3 was used, an experiment similar to that shown in FIG. 12 was performed using the experimental system shown in FIG.

  Since the polymer compound (η) can form a spin coat film by itself, the concentration is 100% by weight.

  The thickness of the spin coat film made of the polymer compound (η) was 0.1 μm.

The intensity of the pump light was set to 10 mJ · cm ⁻² · pulse ⁻¹ .

  In FIG. 17, the result of having averaged the time dependence of the light absorbency in wavelength 365nm to 375nm is plotted.

  From the results shown in FIG. 17, it was possible to observe an initial rapid decrease in absorbance and subsequent monotonous decrease in absorbance with an increase in irradiation time via two-photon absorption.

  Even when the spin coat thin film made of the polymer compound (ι) obtained in Example 4 was used, the experiment similar to that shown in FIG. 12 was conducted using the experimental system shown in FIG.

  Since the polymer compound (ι) can form a spin coat film alone, its concentration is 100% by weight.

  The thickness of the spin coat film made of the polymer compound (ι) was 0.2 μm.

The intensity of the pump light was 19 mJ · cm ⁻² · pulse ⁻¹ .

  FIG. 18 shows the result of plotting the time dependence of absorbance at wavelengths from 415 nm to 425 nm on average.

  From the results shown in FIG. 18, it was possible to observe an initial rapid decrease in absorbance and subsequent monotonous decrease in absorbance with an increase in irradiation time via two-photon absorption.

       The two-photon absorption material of the present invention can be applied to, for example, a three-dimensional optical storage medium in which two-photon absorption thin films are laminated due to its high two-photon absorption coefficient and the feature of causing bond breakage. In addition, the two-photon absorption material of the present invention can be applied to a device that performs three-dimensional drawing by arbitrarily moving a laser beam irradiation spot in a three-dimensional medium in which the two-photon absorption material is uniformly dispersed. Is possible.

It is the schematic which shows the 1st example of the manufacturing process of the organoboron compound contained in the two-photon absorption material of this invention. It is the schematic which shows the 2nd example of the manufacturing process of the organoboron compound contained in the two-photon absorption material of this invention. It is the schematic which shows the 3rd example of the manufacturing process of the organoboron compound contained in the two-photon absorption material of this invention. It is the schematic which shows the 4th example of the manufacturing process of the organoboron compound contained in the two-photon absorption material of this invention. It is a graph which shows the result of having analyzed the organoboron compound obtained in Example 1 by ¹ H-NMR. It is a graph which shows the result of having analyzed the organoboron compound obtained in Example 1 with the mass spectrometer. It is a graph which shows the result of having analyzed the organoboron compound obtained in Example 2 by ¹ H-NMR. It is a graph which shows the result of having analyzed the organoboron compound obtained in Example 2 with the mass spectrometer. It is a graph which shows the time change of the absorption spectrum accompanying UV light irradiation about the thin film which consists of an organoboron compound obtained in Example 1. FIG. It is a schematic diagram which shows the mechanism of a two-photon absorption process. It is a schematic diagram which shows the white light pump probe system used in order to observe a light absorbency about the thin film which consists of a two-photon absorption material of this invention. 4 is a graph showing changes in absorbance with time for a thin film made of an organoboron compound obtained in Example 1. FIG. It is the graph which averaged and plotted the time dependence of the light absorbency in wavelength 350nm to 360nm about the thin film which consists of an organoboron compound obtained in Example 1. FIG. It is a schematic diagram which shows the experimental system of a two-photon absorption process. It is a graph which shows the time dependence of the transmittance | permeability change of probe light about the thin film which consists of an organic boron compound obtained in Example 1. FIG. It is the graph which averaged and plotted the time dependence of the light absorbency in wavelength 350nm to 360nm about the thin film which consists of an organoboron compound obtained in Example 2. FIG. It is the graph which averaged and plotted the time dependence of the light absorbency in wavelength 365nm to 375nm about the thin film which consists of an organoboron compound obtained in Example 3. FIG. It is the graph which averaged the time dependence of the light absorbency in wavelength 415nm to 425nm about the thin film which consists of an organoboron compound obtained in Example 4, and was plotted.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 ... White light pump probe system, 11 ... Titanium sapphire laser, 12 ... Xenon lamp, 13, 14 ... Reflector, 15, 16 ... Condensing lens, 17 ... Detection 18 ... sample, 19 ... pump light, 20 ... probe light.

Claims (16)

two-photon absorbing material seen containing an organic boron compound π-conjugated hydrocarbon units and boron atoms are bonded, the organic boron compound is characterized by being represented by the following formula (4).

(However, in the formula (4), X and X ′ may be the same or different, and the following formula (5) (in the formula (5), o and p represent 0 or 1). , Q represents an integer of 0 or more and 4 or less, A represents the following formula (6) (wherein one hydrogen atom may be substituted with an acyclic substituent); 7) (However, one hydrogen atom may be substituted with an acyclic substituent.); The following formula (8) (However, one hydrogen atom is substituted with an acyclic substituent.) The following formula (9) (however, one hydrogen atom may be substituted with a non-cyclic substituent); the following formula (10) (however, one hydrogen atom) Or may be substituted with an acyclic substituent.); Or the following formula (11) (the broken line represents a double bond as appropriate; J represents an optionally substituted carbon atom or nitrogen atom) , T represents a carbon atom, nitrogen atom, oxygen atom, sulfur atom or single bond which may have a substituent; Q represents a carbon atom which may have a substituent; Represents a nitrogen atom, an oxygen atom or a sulfur atom; M represents an optionally substituted carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a single bond; and L represents an optionally substituted group. Represents a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom; and J and T or T and Q may be combined to form a 1,4-dioxane ring or a benzene ring. A cycloalkyl group having 3 to 10 carbon atoms; an alkenylene group having 2 to 6 carbon atoms; a carbazolyl group; a hydrogen atom substituted with an optionally substituted phenyl group or alkyl group Optionally amino group; pyridini A thiophenyl group which may have a substituent, a phenyl group which may have a substituent, a phenylene group which may have a substituent, and E is one or 2 hydrogen atoms may be substituted with an alkyl group having 1 to 10 carbon atoms; one hydrogen atom is substituted with an alkyl group having 1 to 6 carbon atoms An optionally substituted pyridinyl group; a thiophenyl group in which one hydrogen atom may be substituted with an alkyl group having 1 to 6 carbon atoms; one hydrogen atom having 1 to 6 carbon atoms G represents an alkyl group having 1 to 4 carbon atoms in which a hydrogen atom may be substituted with a halogen atom; a hydrogen atom substituted with a halogen atom 1 or more carbon atoms may be , 12 an alkoxy group, a halogen atom, a cyano group, q number of G may be different even in the same. ). )

comprises an organic boron compound π-conjugated hydrocarbon units and boron atoms are bonded, the two-photon absorption material you characterized in that the organic boron compound represented by the following formula (20).

(In the formula (20), X and X ′ may be the same or different (provided that X ′ may not be present), and m represents an integer of 2 or more and 10,000 or less, The following formula (21) (where, o and p in formula (21) represent 0 or 1, q represents an integer of 0 or more and 4 or less. A represents the following formula (22) (however, 1 Wherein one hydrogen atom may be substituted with an acyclic substituent.); Formula (23) below (wherein one hydrogen atom may be substituted with an acyclic substituent); The following formula (24) (however, one hydrogen atom may be substituted with a non-cyclic substituent); the following formula (25) (where one hydrogen atom is a non-cyclic substituent) The following formula (26) (however, one hydrogen atom may be substituted with an acyclic substituent); or the following formula ( 27) (The broken line represents a double bond as appropriate; J represents an optionally substituted carbon atom, nitrogen atom, oxygen atom or sulfur atom; T represents an optionally substituted carbon atom. Represents a nitrogen atom, an oxygen atom, a sulfur atom or a single bond; Q represents an optionally substituted carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom; M represents an optionally substituted group; Represents a good carbon atom, nitrogen atom, oxygen atom, sulfur atom or single bond; L represents a carbon atom, nitrogen atom, oxygen atom or sulfur atom which may have a substituent; J and T or T and Q Together may form a 1,4-dioxane ring or a benzene ring.) D represents a cycloalkyl group having 3 to 10 carbon atoms; The following alkenylene group; carbazolyl group; hydrogen atom is a substituent A phenyl group which may have an amino group which may be substituted with an alkyl group; a pyridinyl group; a pyrazinylene group; a thiophenyl group which may have a substituent; a phenyl group which may have a substituent Represents a phenylene group which may have a substituent, and E represents a phenyl group in which one or two hydrogen atoms may be substituted with an alkyl group having 1 to 10 carbon atoms; One hydrogen atom may be substituted with an alkyl group having 1 to 6 carbon atoms; one hydrogen atom is substituted with an alkyl group having 1 to 6 carbon atoms; G represents an alkyl group having 1 to 4 carbon atoms in which a hydrogen atom may be substituted with a halogen atom, and G represents 1 carbon atom in which a hydrogen atom may be substituted with a halogen atom. More than 12 Alkoxy group, a halogen atom, a cyano group, q number of G may be different even in the same. ). )

J represents a carbon atom, a nitrogen atom or a sulfur atom which may have a substituent, T represents a carbon atom, a nitrogen atom or a single bond which may have a substituent, and Q represents a substituent. and which may be carbon atoms, a nitrogen atom or a sulfur atom, M is as defined in claim 1 or 2, characterized in that represent carbon atoms which may have a substituent, a nitrogen atom or a single bond Two-photon absorption material. A represents the following formula (36) (wherein one hydrogen atom is an alkyl group having 1 to 4 carbon atoms in which the hydrogen atom may be substituted with a halogen atom; the hydrogen atom is substituted with a halogen atom) An alkoxy group having 1 or more and 12 or less carbon atoms; a phenyl group that may have an alkyl group having 1 or more and 2 or less carbon atoms, or 1 or more carbon atoms; An amino group optionally substituted with 2 or less alkyl groups; -B (Mes) ₂ (where Mes is represented by the following formula (37)); -Si (CH ₃ ) ₃ ; The two-photon absorption material according to claim 1 , wherein the two-photon absorption material is represented by (C ₆ H ₅ ) ₃ ; a cyano group; which may be substituted with a halogen atom.

A represents the following formula (38) (wherein one hydrogen atom is an alkyl group having 1 to 4 carbon atoms in which the hydrogen atom may be substituted with a halogen atom; the hydrogen atom is substituted with a halogen atom) The two-photon absorbing material according to claim 1 , wherein the two-photon absorbing material is represented by the following: an optionally substituted alkoxy group having 1 to 4 carbon atoms.

In A, the following formula (39) (wherein one hydrogen atom may be substituted with an alkyl group having 1 to 4 carbon atoms in which the hydrogen atom may be substituted with a halogen atom). The two-photon absorption material according to claim 1 , wherein the two-photon absorption material is represented by:

A represents the following formula (40) (wherein one hydrogen atom may be substituted with an alkyl group having 1 to 4 carbon atoms in which the hydrogen atom may be substituted with a halogen atom). The two-photon absorption material according to claim 1 , wherein the two-photon absorption material is represented by:

A is represented by the following formula (41) (in which one hydrogen atom may be substituted with an alkyl group having 1 to 8 carbon atoms in which the hydrogen atom may be substituted with a halogen atom). The two-photon absorption material according to claim 1 , wherein the two-photon absorption material is represented by:

A is the following equation (42) (provided that a nitrogen atom, 1 or more carbon atoms may be substituted with alkyl group of 4 or less.) Claim 1, characterized by being represented by or 2 The two-photon absorption material described in 1.

A is the following equation (43) (provided that a nitrogen atom, 1 or more carbon atoms may be substituted with alkyl group of 4 or less.) Claim 1, characterized by being represented by or 2 The two-photon absorption material described in 1.

A is the following equation (44) (provided that a nitrogen atom, 1 or more carbon atoms may be substituted with alkyl group of 4 or less.) Claim 1, characterized by being represented by or 2 The two-photon absorption material described in 1.

D is a cycloalkyl group having 3 to 6 carbon atoms; an alkenylene group having 2 to 3 carbon atoms; an alkyl group having 1 to 10 carbon atoms; or an alkyl group having 1 to 10 carbon atoms, or 1 to 3 carbon atoms A phenyl group which may be substituted with an alkoxy group of 1; a hydrogen atom, a phenyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms or a carbon group having 1 to 4 carbon atoms An amino group optionally substituted with an alkyl group; a thiophenyl group optionally substituted with an alkyl group having 1 to 4 carbon atoms in which one hydrogen atom is substituted; a thiophenylene group The two-photon absorption material according to any one of claims 1 to 11 . E represents a phenyl group in which one or two hydrogen atoms may be substituted with an alkyl group having 1 to 8 carbon atoms; one hydrogen atom has 1 to 4 carbon atoms The two-photon absorption material according to any one of claims 1 to 11 , which represents a thiophenyl group which may be substituted with an alkyl group. The two-photon absorption material according to any one of claims 1 to 11 , wherein G represents a methyl group in which a hydrogen atom may be substituted with a halogen atom; an n-hexoxy group. Equation (4), equation (20) Oite to, X and X'are the following expression (45) - of claim 1 or 2, characterized by being represented by any one of (114) Two-photon absorption material.

Equation (4), equation (20) Oite to, X has the formula (116), or X'is represented by the formula (117), or X has the formula (118), X'has the formula (119) Or X is represented by formula (120), X ′ is represented by formula (121), or X is represented by formula (122), X ′ is represented by formula (123), or X two-photon absorption material according to claim 1 or 2 but is characterized in that the expression (124), X'is represented by the formula (125)

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